CN102046563B - Composition for ferroelectric thin film formation, method for ferroelectric thin film formation, and ferroelectric thin film formed by the method - Google Patents

Composition for ferroelectric thin film formation, method for ferroelectric thin film formation, and ferroelectric thin film formed by the method Download PDF

Info

Publication number
CN102046563B
CN102046563B CN200980119294.7A CN200980119294A CN102046563B CN 102046563 B CN102046563 B CN 102046563B CN 200980119294 A CN200980119294 A CN 200980119294A CN 102046563 B CN102046563 B CN 102046563B
Authority
CN
China
Prior art keywords
dielectric film
strong dielectric
compound
metal
film formation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN200980119294.7A
Other languages
Chinese (zh)
Other versions
CN102046563A (en
Inventor
藤井顺
樱井英章
野口毅
曾山信幸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Materials Corp
Original Assignee
Mitsubishi Materials Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2009059019A external-priority patent/JP5655272B2/en
Priority claimed from JP2009060348A external-priority patent/JP5659457B2/en
Priority claimed from JP2009085830A external-priority patent/JP5293347B2/en
Priority claimed from JP2009085819A external-priority patent/JP5655274B2/en
Priority claimed from JP2009102817A external-priority patent/JP5417962B2/en
Priority claimed from JP2009102815A external-priority patent/JP5526591B2/en
Priority claimed from JP2009105076A external-priority patent/JP5591484B2/en
Priority claimed from JP2009105883A external-priority patent/JP5526593B2/en
Priority claimed from JP2009105885A external-priority patent/JP5591485B2/en
Priority to CN201410553563.3A priority Critical patent/CN104446463B/en
Priority to CN201310273420.2A priority patent/CN103360066B/en
Application filed by Mitsubishi Materials Corp filed Critical Mitsubishi Materials Corp
Publication of CN102046563A publication Critical patent/CN102046563A/en
Publication of CN102046563B publication Critical patent/CN102046563B/en
Application granted granted Critical
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • H10N30/8548—Lead based oxides
    • H10N30/8554—Lead zirconium titanate based
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0209—Multistage baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0406—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0406—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being air
    • B05D3/0413—Heating with air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0433—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a reactive gas
    • B05D3/0453—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0466—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a non-reacting gas
    • B05D3/0473—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a non-reacting gas for heating, e.g. vapour heating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
    • C04B24/42—Organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
    • C04B35/491—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
    • C04B35/491—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT
    • C04B35/493—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT containing also other lead compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/624—Sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/6325—Organic additives based on organo-metallic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1225—Deposition of multilayers of inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1279—Process of deposition of the inorganic material performed under reactive atmosphere, e.g. oxidising or reducing atmospheres
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/14—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances cements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1236—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates
    • H01G4/1245—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates containing also titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/20—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06
    • H01G4/206—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06 inorganic and synthetic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02197—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides the material having a perovskite structure, e.g. BaTiO3
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31691—Inorganic layers composed of oxides or glassy oxides or oxide based glass with perovskite structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40—Capacitors
    • H01L28/55—Capacitors with a dielectric comprising a perovskite structure material
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B12/00—Dynamic random access memory [DRAM] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B53/00—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory capacitors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
    • H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
    • H10N30/077—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition
    • H10N30/078—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition by sol-gel deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • H10N30/8548—Lead based oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/90—Electrical properties
    • C04B2111/92—Electrically insulating materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/441—Alkoxides, e.g. methoxide, tert-butoxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/443—Nitrates or nitrites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/447—Phosphates or phosphites, e.g. orthophosphate, hypophosphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
    • C04B2235/6585—Oxygen containing atmosphere, e.g. with changing oxygen pressures at an oxygen percentage above that of air

Abstract

Disclosed is a composition for ferroelectric thin film formation which is used in the formation of a ferroelectric thin film of one material selected from the group consisting of PLZT, PZT, and PT. The composition for ferroelectric thin film formation is a liquid composition for the formation of a thin film of a mixed composite metal oxide formed of a mixture of a composite metal oxide (A) represented by general formula (1): (PbxLay)(ZrzTi(1-z))O3 [wherein 0.9 < x < 1.3, 0 <= y < 0.1, and 0 <= z < 0.9 are satisfied] with a composite oxide (B) or a carboxylic acid (B) represented by general formula (2): CnH2n+1COOH [wherein 3 <= n <= 7 is satisfied]. The composite oxide (B) contains one or at least two elements selected from the group consisting of P (phosphorus), Si, Ce, and Bi and one or at least two elements selected from the group consisting of Sn, Sm, Nd, and Y (yttrium).

Description

Strong dielectric film forms with the formation method of composition, Strong dielectric film and the Strong dielectric film forming by the method
Technical field
The present invention relates to Strong dielectric film forms with the formation method of composition, Strong dielectric film and the Strong dielectric film forming by the method.
The application based on April 24th, 2009 No. 2009-105883, the Patent of Japanese publication, on March 31st, 2009 is No. 2009-085819, the Patent of Japanese publication, on April 23rd, 2009 is No. 2009-105076, the Patent of Japanese publication, on March 13rd, 2009 is No. 2009-060348, the Patent of Japanese publication, on April 24th, 2009 is No. 2009-105885, the Patent of Japanese publication, on April 21st, 2009 is No. 2009-102817, the Patent of Japanese publication, on March 31st, 2009 is No. 2009-085830, the Patent of Japanese publication, on April 21st, 2009 is advocated right of priority No. 2009-059019 in No. 2009-102815, Patent and on March 12nd, 2009 of Japanese publication in the Patent of Japanese publication, its content is incorporated herein.
background technology
As the manufacture method of strong dielectric film, the alkoxide of each composition metal or organic acid salt are dissolved in the mixing solutions obtaining in polar solvent by common known use, be coated on metal substrate, be dried, form film, be heated to temperature more than crystallized temperature, burn till, thus by thin dielectric film film forming (for example, with reference to patent documentation 1).
In addition, as DRAM or nonvolatile memory purposes, known formation on semiconductor substrate after non-crystalline state or crystalline dielectric film, by the dielectric device manufacture method (for example, referring to patent documentation 2) of gimmick impurities in this dielectric film such as thermal diffusion method or ion implantation, ion doping method.In this patent documentation 2, disclose PZT film as inter metal dielectric film, disclose P (phosphorus) ion as doping agent.By doping P (phosphorus), can improve and equip the DRAM of dielectric capacitor or the storage preserving property of nonvolatile memory.
In addition, as the electrical condenser purposes of semiconductor memory cell, disclose while forming by sol-gel method the strong dielectric film that comprises PZT, generated the two alkoxide of the two alkoxide of plumbous titanium or plumbous zirconium, by above-mentioned reaction product hydrolysis, and carry out high molecular by condensation reaction, modulated raw materials solution, is coated with this material solution, drying coated material solution, form desciccator diaphragm, by the strong dielectric film formation method of this desciccator diaphragm sintering (for example, with reference to patent documentation 3).In this patent documentation 3, the fatigue (minimizing of remnant polarization value) or the stray current that while having recorded the pzt thin film use in order to suppress film forming, have caused because applying voltage reversal can add lanthanum, niobium, iron and so on the 4th metallic element in material solution.The electrical specifications such as according to patent documentation 3, the hydrolysis of each pair of alkoxide and condensation reaction are carried out equably, present level and smooth surface by the pzt thin film of this sol gel solution film forming, and remnant polarization is large, stray current is also little are insufficient, the performance that can meet the demands.
In addition, as the various device purposes of having utilized electric or optical property, the composition that becomes known for forming PLZT Strong dielectric film is the complex metal compound A being represented by PLZT and is selected from Bi, Si, Pb, Ge, Sn, Al, Ga, In, Mg, Ca, Sr, Ba, V, Nb, Ta, Sc, Y, Ti, Zr, Hf, Cr, Mn, Fe, Co, Ni, Zn, Cd, Li, the fluid composition that is used to form mixing composite metal oxide film of the complex metal oxides that the one kind or two or more element in Na and K forms, that the composition (for example, with reference to patent documentation 4) of the compound that forms this metal oxide can provide the ratio of desirable atoms metal ratio to be dissolved in the solution in organic solvent is provided.In this patent documentation 4, by using said composition, while forming Strong dielectric film, even if also can carry out crystallization under the low temperature below 450 DEG C.
And then, as nonvolatile memory purposes, the mixed solution that is used to form Strong dielectric film (for example, with reference to patent documentation 5) that adds Ca or Sr, La in PZT is disclosed.
In addition, while having confirmed to be the PZT film of representative strong dielectric, carry out filming to execute in alive situation, stray current density improves, and then causes puncture of insulation.
Therefore, carry out in the Strong dielectric films such as PZT film, adding trace element, improving the trial of sewing characteristic, but still insufficient (for example, with reference to patent documentation 6,7).
In addition, make the trial that thick film reduces stray current density, but the problem that now exists electrostatic capacity to reduce.
As the countermeasure of the problems referred to above, disclose by the 1at.% cerous nitrate that adulterates in the PZT film of thickness 1 μ m left and right, the relative permittivity that can make the PZT film of non-doping is that 400 left and right degree are increased to 700 left and right, but this relative permittivity is still low, be the inadequate value in practical aspect (for example, with reference to non-patent literature 1).
In addition, while making film, the large stress that the restriction of substrate produces plays a role, and has the problem (for example, with reference to non-patent literature 2) that cannot obtain sufficient relative permittivity.
Therefore, add trial (for example, with reference to non-patent literature 1) micro-, that improve relative permittivity always.
In addition, by filming, electrostatic capacity improves in theory, so also carry out filming, improve the trial of electrostatic capacity always.
In addition, the Bi that also carries out adulterating in PZT improves the trial (for example, with reference to patent documentation 6) of dielectric voltage withstand characteristic.But, in above-mentioned patent documentation 6, only enumerate Bi as doped element, there is not the actual embodiment that carries out doping.In addition, also do not carry out the mensuration of relative permittivity.
In addition, add acetic acid if disclosed in PZT sol gel solution, the stability of the solution in atmosphere improves (for example, with reference to patent documentation 8).Add organic acid acetic if disclosed in PZT sol gel solution, effectively utilize the lattice information of Pt (111) film of substrate, obtain the PZT film (for example, with reference to patent documentation 9) that (111) orientation improves.
But, be not reported in the example that the relative permittivity of PZT film while having added organic acid in PZT sol gel solution improves.
Prior art document
Patent documentation
Patent documentation 1: JP 60-236404 communique (hurdle, 11st row～page 4 lower-left, hurdle, page 3 bottom right the 10th row, hurdle, 10th row～same page lower-left, hurdle, page 5 upper right the 17th row)
Patent documentation 2: Unexamined Patent 5-343641 communique (claim 3,4,8, paragraph [0001], [0065])
Patent documentation 3: Unexamined Patent 7-252664 communique (claim 2,3,7,8, paragraph [0001], [0035], [0117], [0118])
Patent documentation 4: JP 2003-2647 communique (claim 1, paragraph [0001], [0013])
Patent documentation 5: No. 6203608 specification sheets of United States Patent (USP) (FIELD OF THE INVENTION, Claim1)
Patent documentation 6: Unexamined Patent 8-153854 communique (claim 1, claim 3)
Patent documentation 7: JP 2005-217219 communique (claim 5)
Patent documentation 8: Unexamined Patent 11-220185 communique (claim 7, paragraph [0008])
Patent documentation 9: JP 2004-277200 communique (claim 10)
Non-patent literature
Non-patent literature 1:S.B.Majumder, D.C.Agrawal, Y.N.Mohopatra, andR.S.Katiyar, " Effect of Cerium Doping on the Microstructure and Electrical Properties of Sol-Gel Derived Pb1.05 (Zr0.53-dCedTi0.47) O3 (d=10at%) Thin Films ", Materials Science and Engineering, B98,2003, pp.25-32 (Fig.2)
Non-patent literature 2: pottery, 42,175-180 (2007) (p.175 verso the 20th row～22nd row)
summary of the invention
Invent problem to be solved
As described in above-mentioned patent documentation 2, by the P that adulterates in dielectric film (phosphorus), can improve storage preserving property, but this patent documentation 2 is to form after dielectric film, adulterate in the dielectric film the forming gimmick of P (phosphorus), so doping agent heterogeneity in film may import the impurity beyond doping agent, in addition, also may cause the membranous deteriorated of dielectric film.And then, consider multiple operations such as needing heat treatment step, also think that operation becomes numerous and diverse.
In addition, as described in above-mentioned patent documentation 3～5, the technology of developing the characteristic in order to improve dielectric film and add various elements, but while considering Strong dielectric film to be used for the film capacitor purposes of high capacity density, must balance improve well that stray current reduces and dielectric voltage withstand improves two specific characters, or raising relative permittivity.
If the thickness of the Strong dielectric film forming is insufficient, stray current density is high, and puncture of insulation also may occur, and therefore cannot give full play to the performance as electrical condenser.
If make thickness blocked up, there is the problem that cannot obtain sufficient electrostatic capacity.
If reduce the thickness of the Strong dielectric film forming in order to improve electrostatic capacity, stray current density improves, and puncture of insulation also may occur, and cannot give full play to the performance as electrical condenser.The not talkative trial of fully having carried out adding trace element raising relative permittivity.
In above-mentioned patent documentation 4, record and in dielectric film, add various elements, but its objective is reduction crystallized temperature, in addition, only record the result of remnant polarization value, but it is not open in order to be the required high relative dielectric constant of film capacitor purposes of high capacity density, in dielectric film, use which kind of element as doping agent, in addition this doping agent is added to which kind of degree and contribute to relative permittivity to improve.
The object of the invention is to provides the Strong dielectric film of the film capacitor purposes that is applicable to high capacity density to form with the formation method of composition, Strong dielectric film and the Strong dielectric film forming by the method with simple gimmick.
Other objects of the present invention are to be provided and can balance be improved well that stray current reduces and dielectric voltage withstand improves Strong dielectric film formation the formation method of composition, Strong dielectric film and the Strong dielectric film forming by the method for film capacitor purposes two characteristics, that be applicable to high capacity density by simple gimmick.
Other objects of the present invention be by simple gimmick provide have with the relative permittivity of existing Strong dielectric film same degree and, the Strong dielectric film that can obtain film capacitor purposes low-leakage current density, that be applicable to high capacity density forms with the formation method of composition, Strong dielectric film and the Strong dielectric film forming by the method.
Other objects of the present invention are to provide the Strong dielectric film that can significantly improve film capacitor purposes relative permittivity, that be applicable to high capacity density compared with existing Strong dielectric film to form with the formation method of composition, Strong dielectric film and the Strong dielectric film forming by the method by simple gimmick.
For solving the means of problem
[the 1st group]
The 1st mode of the present invention is the Strong dielectric film formation composition that is used to form the a kind of Strong dielectric film that is selected from PLZT, PZT and PT, it is characterized in that, be to be used to form the fluid composition of taking the film that mixes complex metal oxides form, described mixing complex metal oxides is in general formula (1): (Pb xla y) (Zr zti (1-z)) O 3in the complex metal oxides A that (0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9 in formula (1)) represents, mix to comprise and be selected from that the one kind or two or more composite oxides B of P (phosphorus), Si, Ce and Bi obtains
Comprise raw material for forming above-mentioned complex metal oxides A and for the raw material that forms above-mentioned composite oxides B can provide the ratio of the above-mentioned general formula atoms metal that (1) represents ratio to be dissolved in the organometallic compound solution of organic solvent.
A-1 mode of the present invention is the Strong dielectric film formation composition that is used to form the a kind of Strong dielectric film that is selected from PLZT, PZT and PT, it is characterized in that, be to be used to form the fluid composition of taking the film that mixes complex metal oxides form, described mixing complex metal oxides is in general formula (1): (Pb xla y) (Zr zti (1-z)) O 3the composite oxides B that in the complex metal oxides A that (0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9 in formula (1)) represents, mixing comprises P (phosphorus) obtains
Comprise raw material for forming above-mentioned complex metal oxides A and for the raw material that forms above-mentioned composite oxides B can provide the ratio of the above-mentioned general formula atoms metal that (1) represents ratio to be dissolved in the organometallic compound solution of organic solvent.
A-2 mode of the present invention is the invention based on A-1 mode, it is characterized in that, and then is the compound of organic group via its oxygen or nitrogen-atoms and metallic element bonding for forming the raw material of complex metal oxides A.
A-3 mode of the present invention is the invention based on A-2 mode, it is characterized in that, and then be selected from metal alkoxide, metal glycol coordination compound, metal triol coordination compound, metal carboxylate, metal beta-diketon coordination compound, metal beta-diketo-ester coordination compound, metal β-imino-ketone coordination compound and metal amino coordination compound one kind or two or more for forming the raw material of complex metal oxides A.
A-4 mode of the present invention is the invention based on A-1 mode, it is characterized in that, and then is the compound of organic group via its oxygen or nitrogen-atoms and P (phosphorus) element bonding for forming the raw material of composite oxides B.
A-5 mode of the present invention is the invention based on A-4 mode, it is characterized in that, and then be selected from alkoxide cpd, diol compound, three alkylol cpds, carboxylate compounds, beta-diketone compound, beta-diketo-ester compound, β-imino-ketone compound and aminocompound one kind or two or more for forming the raw material of composite oxides B.
A-6 mode of the present invention is the invention based on A-1 mode～A-5 mode, it is characterized in that, and then further contain taking the ratio of 1 mole as 0.2～3 mole of the total metal content with respect in composition the one kind or two or more stabilization agent that is selected from beta-diketon, beta-keto acid, 'beta '-ketoester, alcohol acid, glycol, triol, high carboxylic acid, alkanolamine and polyamine.
A-7 mode of the present invention is the invention based on A-1 mode～A-6 mode, it is characterized in that, and then the mol ratio B/A of composite oxides B and complex metal oxides A is 0 < B/A < 0.2.
A-8 mode of the present invention is the invention based on A-7 mode, it is characterized in that, and then the mol ratio B/A of composite oxides B and complex metal oxides A is 0.003≤B/A≤0.1.
A kind of formation method that A-9 mode of the present invention is Strong dielectric film, it is characterized in that, Strong dielectric film formation based on A-1 mode～A-8 mode is coated to heat resistant substrate with composition, in air, in oxidation atmosphere or the operation that heats in containing water vapor atmosphere carry out 1 time or repeat to the film that can obtain desired thickness, at least adding in final operation hanker or heat after this film is burnt till more than crystallized temperature.
A-10 mode of the present invention is the Strong dielectric film forming by the method based on A-9 mode.
A-11 mode of the present invention is the complex electronic device of the film capacitor with the Strong dielectric film based on A-10 mode, electrical condenser, IPD (Integrated Passive Device), DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer.
A-12 mode of the present invention is the complex electronic device corresponding to the film capacitor above frequency band of 100MHz, that have Strong dielectric film, electrical condenser, IPD, DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer based on A-11 mode.
B-1 mode of the present invention is the Strong dielectric film formation composition that is used to form the a kind of Strong dielectric film that is selected from PLZT, PZT and PT, it is characterized in that, be to be used to form the fluid composition of taking the film that mixes complex metal oxides form, described mixing complex metal oxides is in general formula (1): (Pb xla y) (Zr zti (1-z)) O 3the composite oxides B (complex metal oxides) that in the complex metal oxides A that (0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9 in formula (1)) represents, mixing comprises Si obtains
Comprise raw material for forming complex metal oxides A and for the raw material that forms composite oxides B (complex metal oxides) can provide the ratio of the above-mentioned general formula atoms metal that (1) represents ratio to be dissolved in the organometallic compound solution of organic solvent.
B-2 mode of the present invention is the invention based on B-1 mode, it is characterized in that, and then be the compound of organic group via its oxygen or nitrogen-atoms and metallic element bonding for forming the raw material of complex metal oxides A and composite oxides B (complex metal oxides).
B-3 mode of the present invention is the invention based on B-2 mode, it is characterized in that, and then be selected from metal alkoxide, metal glycol coordination compound, metal triol coordination compound, metal carboxylate, metal beta-diketon coordination compound, metal beta-diketo-ester coordination compound, metal β-imino-ketone coordination compound and metal amino coordination compound one kind or two or more for forming the raw material of complex metal oxides A and composite oxides B (complex metal oxides).
B-4 mode of the present invention is the invention based on B-1 mode～B-3 mode, it is characterized in that, and then further contain taking the ratio of 1 mole as 0.2～3 mole of the total metal content with respect in composition the one kind or two or more stabilization agent that is selected from beta-diketon, beta-keto acid, 'beta '-ketoester, alcohol acid, glycol, triol, high carboxylic acid, alkanolamine and polyamine.
B-5 mode of the present invention is the invention based on B-1 mode～B-4 mode, it is characterized in that, and then organic solvent is be selected from carboxylic acid, alcohol, ester, ketone, ethers, naphthenic, the fragrant same clan and tetrahydrofuran (THF) one kind or two or more.
B-6 mode of the present invention is the invention based on B-1 mode～B-5 mode, it is characterized in that, and then organic solvent contains propylene glycol.
B-7 mode of the present invention is the invention based on B-1 mode～B-6 mode, it is characterized in that, and then the mol ratio B/A of composite oxides B (complex metal oxides) and complex metal oxides A is 0 < B/A < 0.1.
B-8 mode of the present invention is the invention based on B-7 mode, it is characterized in that, and then the mol ratio B/A of composite oxides B (complex metal oxides) and complex metal oxides A is 0.005≤B/A≤0.05.
A kind of formation method that B-9 mode of the present invention is Strong dielectric film, it is characterized in that, Strong dielectric film formation based on B-1 mode～B-8 mode is coated to heat resistant substrate with composition, in air, in oxidation atmosphere or the operation that heats in containing water vapor atmosphere carry out 1 time or repeat to the film that can obtain desired thickness, at least adding in final operation hanker or heat after this film is burnt till more than crystallized temperature.
B-10 mode of the present invention is the Strong dielectric film forming by the method based on B-9 mode.
B-11 mode of the present invention is the complex electronic device of the film capacitor with the Strong dielectric film based on B-10 mode, electrical condenser, IPD (Integrated Passive Device), DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer.
B-12 mode of the present invention is the complex electronic device corresponding to the film capacitor above frequency band of 100MHz, that have Strong dielectric film, electrical condenser, IPD, DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer based on B-11 mode.
C-1 mode of the present invention is the Strong dielectric film formation composition that is used to form the a kind of Strong dielectric film that is selected from PLZT, PZT and PT, it is characterized in that, be to be used to form the fluid composition of taking the film that mixes complex metal oxides form, described mixing complex metal oxides is in general formula (1): (Pb xla y) (Zr zti (1-z)) O 3in the complex metal oxides A that (0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9 in formula (1)) represents, mixing obtains containing the composite oxides B (complex metal oxides) of Ce
The raw material that comprises raw material for forming complex metal oxides A and composite oxides B (complex metal oxides) is can provide the ratio of the above-mentioned general formula atoms metal that (1) represents ratio to be dissolved in the organometallic compound solution of organic solvent.
C-2 mode of the present invention is the invention based on C-1 mode, it is characterized in that, and then be the compound of organic group via its oxygen or nitrogen-atoms and metallic element bonding for forming the raw material of complex metal oxides A and composite oxides B (complex metal oxides).
C-3 mode of the present invention is the invention based on C-2 mode, it is characterized in that, and then be selected from metal alkoxide, metal glycol coordination compound, metal triol coordination compound, metal carboxylate, metal beta-diketon coordination compound, metal beta-diketo-ester coordination compound, metal β-imino-ketone coordination compound and metal amino coordination compound one kind or two or more for forming the raw material of complex metal oxides A and composite oxides B (complex metal oxides).
C-4 mode of the present invention is the invention based on C-1 mode～C-3 mode, it is characterized in that, and then further contain taking the ratio of 1 mole as 0.2～3 mole of the total metal content with respect in composition the one kind or two or more stabilization agent that is selected from beta-diketon, beta-keto acid, 'beta '-ketoester, alcohol acid, glycol, triol, high carboxylic acid, alkanolamine and polyamine.
C-5 mode of the present invention is the invention based on C-1 mode～C-4 mode, it is characterized in that, and then the mol ratio B/A of composite oxides B (complex metal oxides) and complex metal oxides A is 0 < B/A < 0.05.
C-6 mode of the present invention is the invention based on C-5 mode, it is characterized in that, and then the mol ratio B/A of composite oxides B (complex metal oxides) and complex metal oxides A is 0.005≤B/A≤0.03.
A kind of formation method that C-7 mode of the present invention is Strong dielectric film, it is characterized in that, Strong dielectric film formation based on C-1 mode～C-6 mode is coated to heat resistant substrate with composition, in air, in oxidation atmosphere or the operation that heats in containing water vapor atmosphere carry out 1 time or repeat to the film that can obtain desired thickness, at least adding in final operation hanker or heat after this film is burnt till more than crystallized temperature.
C-8 mode of the present invention is the Strong dielectric film forming by the method based on C-7 mode.
C-9 mode of the present invention is the complex electronic device of the film capacitor with the Strong dielectric film based on C-8 mode, electrical condenser, IPD (Integrated PassiveDevice), DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer.
C-10 mode of the present invention is the complex electronic device corresponding to the film capacitor above frequency band of 100MHz, that have Strong dielectric film, electrical condenser, IPD, DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer based on C-9 mode.
D-1 mode of the present invention is the Strong dielectric film formation composition that is used to form the a kind of Strong dielectric film that is selected from PLZT, PZT and PT, it is characterized in that, be to be used to form the fluid composition of taking the film that mixes complex metal oxides form, described mixing complex metal oxides is in general formula (1): (Pb xla y) (Zr zti (1-z)) O 3the composite oxides B (complex metal oxides) that in the complex metal oxides A that (0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9 in formula (1)) represents, mixing comprises Bi obtains
Comprise raw material for forming complex metal oxides A and for the raw material that forms composite oxides B (complex metal oxides) can provide the ratio of the above-mentioned general formula atoms metal that (1) represents ratio to be dissolved in the organometallic compound solution of organic solvent.
D-2 mode of the present invention is the invention based on D-1 mode, it is characterized in that, and then described composition is that raw material for forming complex metal oxides A and composite oxides B (complex metal oxides) is the Strong dielectric film formation composition of organic group via the compound of its oxygen or nitrogen-atoms and metallic element bonding.
D-3 mode of the present invention is the invention based on D-2 mode, it is characterized in that, and then described composition is the one kind or two or more Strong dielectric film formation composition that raw material for forming complex metal oxides A and composite oxides B (complex metal oxides) is selected from metal alkoxide, metal glycol coordination compound, metal triol coordination compound, metal carboxylate, metal beta-diketon coordination compound, metal beta-diketo-ester coordination compound, metal β-imino-ketone coordination compound and metal amino coordination compound.
D-4 mode of the present invention is the invention based on D-1 mode～D-3 mode, it is characterized in that, and then described composition is the Strong dielectric film formation composition that further contains the one kind or two or more stabilization agent that is selected from beta-diketon, beta-keto acid, 'beta '-ketoester, alcohol acid, glycol, triol, high carboxylic acid, alkanolamine and polyamine taking the ratio of 1 mole as 0.2～3 mole of the total metal content with respect in composition.
D-5 mode of the present invention is the invention based on D-1 mode～D-4 mode, it is characterized in that, and then the mol ratio B/A of composite oxides B (complex metal oxides) and complex metal oxides A is 0 < B/A < 0.2.
D-6 mode of the present invention is the invention based on D-5 mode, it is characterized in that, and then the mol ratio B/A of composite oxides B (complex metal oxides) and complex metal oxides A is 0.005≤B/A≤0.1.
A kind of formation method that D-7 mode of the present invention is Strong dielectric film, it is characterized in that, Strong dielectric film formation based on D-1 mode～D-6 mode is coated to heat resistant substrate with composition, in air, in oxidation atmosphere or the operation that heats in containing water vapor atmosphere carry out 1 time or repeat to the film that can obtain desired thickness, at least adding in final operation hanker or heat after this film is burnt till more than crystallized temperature.
D-8 mode of the present invention is the Strong dielectric film forming by the method based on D-7 mode.
D-9 mode of the present invention is the complex electronic device of the film capacitor with the Strong dielectric film based on D-8 mode, electrical condenser, IPD (Integrated Passive Device), DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer.
D-10 mode of the present invention is the complex electronic device corresponding to the film capacitor above frequency band of 100MHz, that have Strong dielectric film, electrical condenser, IPD, DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer based on D-9 mode.
[the 2nd group]
The 2nd prescription formula of the present invention is the Strong dielectric film formation composition that is used to form the a kind of Strong dielectric film that is selected from PLZT, PZT and PT, it is characterized in that, be to be used to form the fluid composition of taking the film that mixes complex metal oxides form, described mixing complex metal oxides is in general formula (1): (Pb xla y) (Zr zti (1-z)) O 3in the complex metal oxides A that (0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9 in formula (1)) represents, mix to comprise and be selected from that the one kind or two or more composite oxides B of Sn, Sm, Nd and Y (yttrium) obtains
For the ratio that forms the raw material of above-mentioned complex metal oxides A and be the atoms metal ratio that above-mentioned general formula (1) can be provided represent for the raw material that forms above-mentioned composite oxides B, and, when composite oxides B contains Sn, the mol ratio B/A that comprises composite oxides B and complex metal oxides A is dissolved in the organometallic compound solution in organic solvent in the scope of 0.003≤B/A≤0.05, composite oxides B contains and is selected from Sm, when Nd and Y (yttrium) one kind or two or more, the mol ratio B/A that comprises composite oxides B and complex metal oxides A is that the scope of 0.005≤B/A < 0.03 is dissolved in the organometallic compound solution in organic solvent interiorly.
E-1 mode of the present invention is the Strong dielectric film formation composition that is used to form the a kind of Strong dielectric film that is selected from PLZT, PZT and PT, it is characterized in that, be to be used to form the fluid composition of taking the film that mixes complex metal oxides form, described mixing complex metal oxides is in general formula (1): (Pb xla y) (Zr zti (1-z)) O 3the composite oxides B (complex metal oxides) that in the complex metal oxides A that (0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9 in formula (1)) represents, mixing comprises Sn obtains
Comprise raw material for forming above-mentioned complex metal oxides A and above-mentioned for the raw material that forms composite oxides B (complex metal oxides) taking can provide the above-mentioned general formula atoms metal that (1) represents ratio ratio and, the mol ratio B/A of composite oxides B and complex metal oxides A as the scope of 0.003≤B/A≤0.05 interior be dissolved in the organometallic compound solution of organic solvent.
E-2 mode of the present invention is the invention based on E-1 mode, it is characterized in that, and then be the compound of organic group via its oxygen or nitrogen-atoms and metallic element bonding for forming the raw material of complex metal oxides A and composite oxides B (complex metal oxides).
E-3 mode of the present invention is the invention based on E-2 mode, it is characterized in that, and then be selected from metal alkoxide, metal glycol coordination compound, metal triol coordination compound, metal carboxylate, metal beta-diketon coordination compound, metal beta-diketo-ester coordination compound, metal β-imino-ketone coordination compound and metal amino coordination compound one kind or two or more for forming the raw material of complex metal oxides A and composite oxides B (complex metal oxides).
E-4 mode of the present invention is the invention based on E-1 mode～E-3 mode, it is characterized in that, and then further contain taking the ratio of 1 mole as 0.2～3 mole of the total metal content with respect in composition the one kind or two or more stabilization agent that is selected from beta-diketon, beta-keto acid, 'beta '-ketoester, alcohol acid, glycol, triol, high carboxylic acid, alkanolamine and polyamine.
A kind of formation method that E-5 mode of the present invention is Strong dielectric film, it is characterized in that, Strong dielectric film formation based on E-1 mode～E-4 mode is coated to heat resistant substrate with composition, in air, in oxidation atmosphere or the operation that heats in containing water vapor atmosphere carry out 1 time or repeat to the film that can obtain desired thickness, at least adding in final operation hanker or heat after this film is burnt till more than crystallized temperature.
E-6 mode of the present invention is the Strong dielectric film forming by the method based on E-5 mode.
E-7 mode of the present invention is the complex electronic device of the film capacitor with the Strong dielectric film based on E-6 mode, electrical condenser, IPD (Integrated Passive Device), DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer.
E-8 mode of the present invention is the complex electronic device corresponding to the film capacitor above frequency band of 100MHz, that have Strong dielectric film, electrical condenser, IPD, DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer based on E-7 mode.
F-1 mode of the present invention is the Strong dielectric film formation composition that is used to form the a kind of Strong dielectric film that is selected from PLZT, PZT and PT, it is characterized in that, be to be used to form the fluid composition of taking the film that mixes complex metal oxides form, described mixing complex metal oxides is in general formula (1): (Pb xla y) (Zr zti (1-z)) O 3the composite oxides B (complex metal oxides) that in the complex metal oxides A that (0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9 in formula (1)) represents, mixing comprises Sm obtains
Comprise raw material for forming complex metal oxides A and for the raw material that forms composite oxides B (complex metal oxides) taking can provide the above-mentioned general formula atoms metal that (1) represents ratio ratio and, the mol ratio B/A of B and A as the scope of 0.005≤B/A < 0.03 interior be dissolved in the organometallic compound solution of organic solvent.
F-2 mode of the present invention is the invention based on F-1 mode, it is characterized in that, and then described composition is that raw material for forming complex metal oxides A and composite oxides B (complex metal oxides) is the Strong dielectric film formation composition of organic group via the compound of its oxygen or nitrogen-atoms and metallic element bonding.
F-3 mode of the present invention is the invention based on F-2 mode, it is characterized in that, and then described composition is the one kind or two or more Strong dielectric film formation composition that raw material for forming complex metal oxides A and composite oxides B (complex metal oxides) is selected from metal alkoxide, metal glycol coordination compound, metal triol coordination compound, metal carboxylate, metal beta-diketon coordination compound, metal beta-diketo-ester coordination compound, metal β-imino-ketone coordination compound and metal amino coordination compound.
F-4 mode of the present invention is the invention based on F-1 mode～F-3 mode, it is characterized in that, and then described composition is the Strong dielectric film formation composition that further contains the one kind or two or more stabilization agent that is selected from beta-diketon, beta-keto acid, 'beta '-ketoester, alcohol acid, glycol, triol, high carboxylic acid, alkanolamine and polyamine taking the ratio of 1 mole as 0.2～3 mole of the total metal content with respect in composition.
A kind of formation method that F-5 mode of the present invention is Strong dielectric film, it is characterized in that, Strong dielectric film formation based on F-1 mode～F-4 mode is coated to heat resistant substrate with composition, in air, in oxidation atmosphere or the operation that heats in containing water vapor atmosphere carry out 1 time or repeat to the film that can obtain desired thickness, at least adding in final operation hanker or heat after this film is burnt till more than crystallized temperature.
F-6 mode of the present invention is the Strong dielectric film forming by the method based on F-5 mode.
F-7 mode of the present invention is the complex electronic device of the film capacitor with the Strong dielectric film based on F-6 mode, electrical condenser, IPD (Integrated Passive Device), DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer.
F-8 mode of the present invention is the complex electronic device corresponding to the film capacitor above frequency band of 100MHz, that have Strong dielectric film, electrical condenser, IPD, DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer based on F-7 mode.
G-1 mode of the present invention is the Strong dielectric film formation composition that is used to form the a kind of Strong dielectric film that is selected from PLZT, PZT and PT, it is characterized in that, be to be used to form the fluid composition of taking the film that mixes complex metal oxides form, described mixing complex metal oxides is in general formula (1): (Pb xla y) (Zr zti (1-z)) O 3the composite oxides B (complex metal oxides) that in the complex metal oxides A that (0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9 in formula (1)) represents, mixing comprises Nd obtains
Comprise raw material for forming complex metal oxides A and for the raw material that forms composite oxides B (complex metal oxides) taking can provide the above-mentioned general formula atoms metal that (1) represents ratio ratio and, the mol ratio B/A of B and A as the scope of 0.005≤B/A < 0.03 interior be dissolved in the organometallic compound solution of organic solvent.
G-2 mode of the present invention is the invention based on G-1 mode, it is characterized in that, and then described composition is that raw material for forming complex metal oxides A and composite oxides B (complex metal oxides) is the Strong dielectric film formation composition of organic group via the compound of its oxygen or nitrogen-atoms and metallic element bonding.
G-3 mode of the present invention is the invention based on G-2 mode, it is characterized in that, and then described composition is the one kind or two or more Strong dielectric film formation composition that raw material for forming complex metal oxides A and composite oxides B (complex metal oxides) is selected from metal alkoxide, metal glycol coordination compound, metal triol coordination compound, metal carboxylate, metal beta-diketon coordination compound, metal beta-diketo-ester coordination compound, metal β-imino-ketone coordination compound and metal amino coordination compound.
G-4 mode of the present invention is the invention based on G-1 mode～G-3 mode, it is characterized in that, and then described composition is the Strong dielectric film formation composition that further contains the one kind or two or more stabilization agent that is selected from beta-diketon, beta-keto acid, 'beta '-ketoester, alcohol acid, glycol, triol, high carboxylic acid, alkanolamine and polyamine taking the ratio of 1 mole as 0.2～3 mole of the total metal content with respect in composition.
A kind of formation method that G-5 mode of the present invention is Strong dielectric film, it is characterized in that, Strong dielectric film formation based on G-1 mode～G-4 mode is coated to heat resistant substrate with composition, in air, in oxidation atmosphere or the operation that heats in containing water vapor atmosphere carry out 1 time or repeat to the film that can obtain desired thickness, at least adding in final operation hanker or heat after this film is burnt till more than crystallized temperature.
G-6 mode of the present invention is the Strong dielectric film forming by the method based on G-5 mode.
G-7 mode of the present invention is the complex electronic device of the film capacitor with the Strong dielectric film based on G-6 mode, electrical condenser, IPD (Integrated Passive Device), DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer.
G-8 mode of the present invention is the complex electronic device corresponding to the film capacitor above frequency band of 100MHz, that have Strong dielectric film, electrical condenser, IPD, DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer based on G-7 mode.
H-1 mode of the present invention is the Strong dielectric film formation composition that is used to form the a kind of Strong dielectric film that is selected from PLZT, PZT and PT, it is characterized in that, be to be used to form the fluid composition of taking the film that mixes complex metal oxides form, described mixing complex metal oxides is in general formula (1): (Pb xla y) (Zr zti (1-z)) O 3the composite oxides B (complex metal oxides) that in the complex metal oxides A that (0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9 in formula (1)) represents, mixing comprises Y (yttrium) obtains
Comprise raw material for forming complex metal oxides A and for the raw material that forms composite oxides B (complex metal oxides) taking can provide the above-mentioned general formula atoms metal that (1) represents ratio ratio and, the mol ratio B/A of B and A as the scope of 0.005≤B/A < 0.03 interior be dissolved in the organometallic compound solution of organic solvent.
H-2 mode of the present invention is the invention based on H-1 mode, it is characterized in that, and then described composition is that raw material for forming complex metal oxides A and composite oxides B (complex metal oxides) is the Strong dielectric film formation composition of organic group via the compound of its oxygen or nitrogen-atoms and metallic element bonding.
H-3 mode of the present invention is the invention based on H-2 mode, it is characterized in that, and then described composition is the one kind or two or more Strong dielectric film formation composition that raw material for forming complex metal oxides A and composite oxides B (complex metal oxides) is selected from metal alkoxide, metal glycol coordination compound, metal triol coordination compound, metal carboxylate, metal beta-diketon coordination compound, metal beta-diketo-ester coordination compound, metal β-imino-ketone coordination compound and metal amino coordination compound.
H-4 mode of the present invention is the invention based on H-1 mode～H-3 mode, it is characterized in that, and then described composition is the Strong dielectric film formation composition that further contains the one kind or two or more stabilization agent that is selected from beta-diketon, beta-keto acid, 'beta '-ketoester, alcohol acid, glycol, triol, high carboxylic acid, alkanolamine and polyamine taking the ratio of 1 mole as 0.2～3 mole of the total metal content with respect in composition.
A kind of formation method that H-5 mode of the present invention is Strong dielectric film, it is characterized in that, Strong dielectric film formation based on H-1 mode～H-4 mode is coated to heat resistant substrate with composition, in air, in oxidation atmosphere or the operation that heats in containing water vapor atmosphere carry out 1 time or repeat to the film that can obtain desired thickness, at least adding in final operation hanker or heat after this film is burnt till more than crystallized temperature.
H-6 mode of the present invention is the Strong dielectric film forming by the method based on H-5 mode.
H-7 mode of the present invention is the complex electronic device of the film capacitor with the Strong dielectric film based on H-6 mode, electrical condenser, IPD (Integrated Passive Device), DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer.
H-8 mode of the present invention is the complex electronic device corresponding to the film capacitor above frequency band of 100MHz, that have Strong dielectric film, electrical condenser, IPD, DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer based on H-7 mode.
[the 3rd group]
I-1 mode of the present invention is the Strong dielectric film formation composition that is used to form the a kind of Strong dielectric film that is selected from PLZT, PZT and PT, it is characterized in that, be to be used to form the fluid composition of taking the film that mixes complex metal oxides form, described mixing complex metal oxides is in general formula (1): (Pb xla y) (Zr zti (1-z)) O 3in the complex metal oxides A that (0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9 in formula (1)) represents, mix general formula (2) C nh 2n+1cOOH (wherein, 3≤n≤7) represents and coordination can obtain on above-mentioned metal time following formula (3) structure, carboxylic acid B obtains,
The mode in the scope of 0 < B/A < 0.2 is dissolved in the organometallic compound solution of organic solvent taking the mol ratio B/A of carboxylic acid B and complex metal oxides A to comprise raw material for forming complex metal oxides A and carboxylic acid B.
[changing 1]
Wherein, in formula (3), meeting above-mentioned general formula (2) C nh 2n+1in the scope of the n of COOH, R1, R2, R3, R4, R5, R6 represent hydrogen, methyl or ethyl, and M represents Pb, La, Zr or Ti, and m represents the valence mumber of M.
I-2 mode of the present invention is the invention based on I-1 mode, it is characterized in that, and then described composition is that raw material for forming complex metal oxides A is the Strong dielectric film formation composition of organic group via the compound of its oxygen or nitrogen-atoms and metallic element bonding.
I-3 mode of the present invention is the invention based on I-2 mode, it is characterized in that, and then described composition is the one kind or two or more Strong dielectric film formation composition that raw material for forming complex metal oxides A is selected from metal alkoxide, metal glycol coordination compound, metal triol coordination compound, metal carboxylate, metal beta-diketon coordination compound, metal beta-diketo-ester coordination compound, metal β-imino-ketone coordination compound and metal amino coordination compound.
I-4 mode of the present invention is the invention based on I-1 mode～I-3 mode, it is characterized in that, and then described composition is the Strong dielectric film formation composition that further contains the one kind or two or more stabilization agent that is selected from beta-diketon, beta-keto acid, 'beta '-ketoester, alcohol acid, glycol, triol, alkanolamine and polyamine taking the ratio of 1 mole as 0.2～3 mole of the total metal content with respect in composition.
I-5 mode of the present invention is the invention based on I-1 mode～I-4 mode, it is characterized in that, and then the mol ratio B/A of carboxylic acid B and complex metal oxides A is 0.001≤B/A≤0.1.
I-6 mode of the present invention is the invention based on I-5 mode, it is characterized in that, and then the mol ratio B/A of carboxylic acid B and complex metal oxides A is 0.03≤B/A≤0.1.
I-7 mode of the present invention is the invention based on I-6 mode, it is characterized in that, and then the mol ratio B/A of carboxylic acid B and complex metal oxides A is 0.05≤B/A≤0.1.
A kind of formation method that I-8 mode of the present invention is Strong dielectric film, it is characterized in that, Strong dielectric film formation based on I-1 mode～I-7 mode is coated to heat resistant substrate with composition, in air, in oxidation atmosphere or the operation that heats in containing water vapor atmosphere carry out 1 time or repeat to the film that can obtain desired thickness, at least adding in final operation hanker or heat after this film is burnt till more than crystallized temperature.
I-9 mode of the present invention is the Strong dielectric film forming by the method based on I-8 mode.
I-10 mode of the present invention is the complex electronic device of the film capacitor with Strong dielectric film based on I-9 mode, electrical condenser, IPD (Integrated Passive Device), DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer.
I-11 mode of the present invention is the complex electronic device corresponding to the film capacitor above frequency band of 100MHz, that have Strong dielectric film, electrical condenser, IPD, DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer based on I-10 mode.
Invention effect
The Strong dielectric film formation of the application of the invention forms Strong dielectric film with composition, can obtain with simple method the Strong dielectric film of the film capacitor purposes that is applicable to high capacity density.
As other effects of the present invention, the Strong dielectric film that can enumerate the application of the invention forms and forms Strong dielectric film with composition, can be balanced and improve well that stray current reduces and dielectric voltage withstand improves the Strong dielectric film of the film capacitor purposes of the applicable high capacity density of two characteristics with simple method.
As other effects of the present invention, the Strong dielectric film that can enumerate the application of the invention forms and forms Strong dielectric film with composition, can with simple method obtain having with the relative permittivity of existing Strong dielectric film same degree and, can obtain low-leakage current density, be applicable to the Strong dielectric film of the film capacitor purposes of high capacity density.Therefore,, while being with the stray current density of current same degree, further filming, can obtain higher relative permittivity.
As other effects of the present invention, the Strong dielectric film formation composition that can enumerate the application of the invention forms Strong dielectric film, can obtain with simple method the Strong dielectric film of the film capacitor purposes of the applicable high capacity density that has significantly improved relative permittivity compared with existing Strong dielectric film.
brief description of the drawings
The figure of the stray current density while applying 5V in [Fig. 1] expression embodiment A-1～embodiment A-29, Comparative examples A-1～Comparative examples A-8 and the relation of P (phosphorus) addition.
The figure of the stray current density while applying 20V in [Fig. 2] expression embodiment A-1～embodiment A-29, Comparative examples A-1～Comparative examples A-8 and the relation of P (phosphorus) addition.
The figure of the stray current density while applying 50V in [Fig. 3] expression embodiment A-1～embodiment A-29, Comparative examples A-1～Comparative examples A-8 and the relation of P (phosphorus) addition.
[Fig. 4] represents to apply in embodiment A-1～embodiment A-29, Comparative examples A-1～Comparative examples A-8 figure of the relation of dielectric voltage withstand and P (phosphorus) addition.
[Fig. 5] represents the I-V performance chart of the film obtaining in Embodiment B-3.
[Fig. 6] represents the I-V performance chart of the film obtaining in Embodiment B-8.
[Fig. 7] represents the I-V performance chart of the film obtaining in Embodiment B-13.
[Fig. 8] represents the I-V performance chart of the film obtaining in Embodiment B-18.
[Fig. 9] represents the I-V performance chart of the film obtaining in Embodiment B-23.
[Figure 10] represents the I-V performance chart of the film obtaining in comparative example B-1.
[Figure 11] represents the I-V performance chart of the film obtaining in comparative example B-2.
The figure of the relative permittivity ε r in [Figure 12] expression embodiment E-1～embodiment E-8, Comparative Example E-1 and the relation of Sn addition.
[Figure 13] represents the figure of the C-V curve in Comparative Example E-1.
[Figure 14] represents the figure of the C-V curve in embodiment E-2.
[Figure 15] represents the figure of the C-V curve in embodiment E-7.
embodiment
The following describes this embodiment.
[the 1st group]
Strong dielectric film formation in the 1st group of the present invention is the composition that is used to form the a kind of Strong dielectric film that is selected from PLZT, PZT and PT with composition.The Strong dielectric film that uses said composition to form is taked in general formula (1): (Pb xla y) (Zr zti (1-z)) O 3in the complex metal oxides A that (0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9 in formula (1)) represents, mix the mixing complex metal oxides form that comprises the one kind or two or more composite oxides B that is selected from P (phosphorus), Si, Ce and Bi.It should be noted that, y ≠ 0 of above-mentioned formula (1) and z ≠ 0 o'clock are PLZT, and y=0 and z ≠ 0 o'clock are PZT, are PT when y=0 and z=0.Said composition comprise raw material for forming complex metal oxides A and for the raw material that forms composite oxides B can provide the ratio of the above-mentioned general formula atoms metal that (1) represents ratio to be dissolved in the organometallic compound solution of organic solvent.
In addition, comprise while being selected from Si, Ce and Bi one kind or two or more in composite oxides B, composite oxides B is complex metal oxides.
When composite oxides B contains P (phosphorus), complex metal oxides A with the preferred organic group of raw material via its oxygen or nitrogen atom bonding the compound on each metallic element of Pb, La, Zr and Ti.For example can enumerate and be selected from the one kind or two or more of metal alkoxide, metal glycol coordination compound, metal triol coordination compound, metal carboxylate, metal beta-diketon coordination compound, metal beta-diketo-ester coordination compound, metal β-imino-ketone coordination compound and metal amino coordination compound.Particularly preferred compound is metal alkoxide, its partial hydrolystate, organic acid salt.Wherein, as Pb compound, La compound, can enumerate the alkoxide such as organic acid salt, diisopropanol lead such as acetate (lead acetate, lanthanum acetate).As Ti compound, can enumerate the alkoxide such as titanium tetraethoxide, titanium tetraisopropylate, four butanols titaniums, dimethoxy diisopropanol titanium.As Zr compound, the preferably alcohol salt same with above-mentioned Ti compound.Can directly to use metal alkoxide, but to decompose in order promoting, also can use its partial hydrolystate.
When composite oxides B contains P (phosphorus), composite oxides B with the preferred organic group of raw material via its oxygen or nitrogen atom bonding the compound on P (phosphorus) element.For example can enumerate and be selected from the one kind or two or more of alkoxide cpd, diol compound, three alkylol cpds, carboxylate compounds, beta-diketone compound, beta-diketo-ester compound, β-imino-ketone compound and aminocompound.Particularly preferred compound is alkoxide cpd, its partial hydrolystate.
Composite oxides B is while containing the one kind or two or more complex metal oxides that is selected from Si, Ce and Bi, complex metal oxides A with raw material and the preferred organic group of composite oxides B raw material via its oxygen or nitrogen atom bonding the compound on each metallic element of Pb, La, Zr, Ti, Si, Ce and Bi.For example can enumerate and be selected from the one kind or two or more of metal alkoxide, metal glycol coordination compound, metal triol coordination compound, metal carboxylate, metal beta-diketon coordination compound, metal beta-diketo-ester coordination compound, metal β-imino-ketone coordination compound and metal amino coordination compound.Particularly preferred compound is metal alkoxide, its partial hydrolystate, organic acid salt.Wherein, as Pb compound, La compound, can enumerate the alkoxide such as organic acid salt, diisopropanol lead such as acetate (lead acetate, lanthanum acetate).As Si compound, can enumerate the metal beta-diketon coordination compoundes such as alkoxide, four (methyl ethyl diketone) silicon such as the organic acid salt such as 2 ethyl hexanoic acid silicon, 2 Ethylbutanoic acid silicon, tetraethoxide silicon, four propyl carbinol silicon.As Ce compound, can enumerate the metal beta-diketon coordination compoundes such as alkoxide, tri acetylacetonato cerium such as the organic acid salt such as 2 ethyl hexanoic acid cerium, 2 Ethylbutanoic acid cerium, three propyl carbinol ceriums, three ethanol ceriums.As Bi compound, can enumerate the metal beta-diketon coordination compoundes such as alkoxide, four (methyl heptadione) bismuth such as the organic acid salt such as 2 ethyl hexanoic acid bismuth, 2 Ethylbutanoic acid bismuth, three Virahol bismuths, three tertiary amyl alcohol bismuths.As Ti compound, can enumerate the alkoxide such as titanium tetraethoxide, titanium tetraisopropylate, four butanols titaniums, dimethoxy diisopropanol titanium.As Zr compound, the preferably alcohol salt same with above-mentioned Ti compound.Can directly to use metal alkoxide, but to decompose in order promoting, can use its partial hydrolystate.
In order to modulate Strong dielectric film formation composition of the present invention, by above-mentioned raw materials with the ratio solvent that is equivalent to desirable Strong dielectric film composition in suitable solvent, be modulated into the concentration that is applicable to coating.
When composite oxides B contains P (phosphorus), be adjusted to the mol ratio B/A of composite oxides B and complex metal oxides A in the scope of 0 < B/A < 0.2.As long as in above-mentioned scope, just can balance improve well two characteristics as the stray current reduction of effect of the present invention and the Strong dielectric film of dielectric voltage withstand raising.It should be noted that, if exceed higher limit, the deteriorated unfavorable condition of relative permittivity occurs.Wherein, be particularly preferably 0.003≤B/A≤0.1.
When composite oxides B contains Si, be adjusted to the mol ratio B/A of composite oxides B and complex metal oxides A in the scope of 0 < B/A < 0.1.As long as in above-mentioned scope, just can obtain as the low-leakage current density of effect of the present invention and, high dielectric voltage withstand.Wherein, be particularly preferably 0.005≤B/A≤0.05.
When composite oxides B contains Ce, be adjusted to the mol ratio B/A of composite oxides B and complex metal oxides A in the scope of 0 < B/A < 0.05.As long as in above-mentioned scope, just can have as effect of the present invention and relative permittivity existing Strong dielectric film same degree, and obtain low-leakage current density.It should be noted that, if exceed higher limit, the deteriorated unfavorable condition of relative permittivity occurs.Wherein, be particularly preferably 0.005≤B/A≤0.03.
When composite oxides B contains Bi, be adjusted to the mol ratio B/A of composite oxides B and complex metal oxides A in the scope of 0 < B/A < 0.2.As long as in above-mentioned scope, just can significantly improve relative permittivity compared with existing Strong dielectric film.It should be noted that, when not enough lower value or while exceeding higher limit, obtain not having when not adding bismuth the result of large difference, be not suitable for the film capacitor purposes of high capacity density.Wherein, be particularly preferably 0.005≤B/A≤0.1.
The Strong dielectric film that uses in the 1st group forms and suitably determines corresponding to the raw material of use with the solvent of composition, conventionally can use carboxylic acid, alcohol, ester, ketone (such as acetone, methyl ethyl ketone), ethers (such as dimethyl ether, Anaesthetie Ether), naphthenic (such as hexanaphthene, hexalin), the fragrant same clan (such as benzene,toluene,xylene), in addition tetrahydrofuran (THF) etc. or their mixed solvent of more than two kinds.In addition, when composite oxides B contains Si, also can use propylene glycol.
As carboxylic acid, particularly preferably use butanic acid, α-methyl butyric acid, isovaleric acid, 2 Ethylbutanoic acid, 2,2-acid dimethyl, 3,3-acid dimethyl, 2,3-acid dimethyl, 3 methylvaleric acid, 4-methylvaleric acid, 2-ethyl valeric acid, 3-ethyl valeric acid, 2,2-dimethyl valeric acid, 3,3-dimethyl valeric acid, 2,3-dimethyl valeric acid, 2 ethyl hexanoic acid, 3-thylhexoic acid.
In addition, as ester, preferably use ethyl acetate, propyl acetate, n-butyl acetate, sec-butyl acetate, tert.-butyl acetate, isobutyl acetate, n-amyl acetate, sec-amyl acetate, tert.-amyl acetate, Isoamyl Acetate FCC, as alcohol, preferably use 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, iso-butyl alcohol, 1-amylalcohol, 2-amylalcohol, 2-methyl-2-amylalcohol, 2-methyl cellosolve.
It should be noted that, Strong dielectric film formation is preferably 0.1～20 quality % left and right by the total concn of the organometallic compound in the organometallic compound solution of composition in metal oxide conversion amount.
In this organometallic compound solution, as required, as stabilization agent, can add 0.2～3 left and right beta-diketon class (for example methyl ethyl diketone in (stabilization agent molecule number)/(atoms metal number), seven fluorine butyryl radicals valeryl methane, two valeryl methane, trifluoroacetylacetone, benzoyl acetone etc.), beta-keto acid class (for example etheric acid, propionyl acetic acid, benzoyl acetic acid etc.), 'beta '-ketoester class (the methyl esters of for example above-mentioned ketone acid, propyl ester, the lower alkyl esters classes such as butyl ester), hydroxyl acids (for example lactic acid, oxyacetic acid, alpha-hydroxybutyric acid, Whitfield's ointment etc.), the lower alkyl esters class of above-mentioned alcohol acid, quinones (oxyketone) (for example diacetone alcohol, acetoin etc.), glycol, triol, high carboxylic acid, alkanol amine (for example diethanolamine, trolamine, monoethanolamine), polyamine etc.
In the present invention, by the organometallic compound solution of above-mentioned modulation by filtration treatment etc. except degranulation, the preferred every 1mL solution of number of the particle of particle diameter 0.5 μ m above (particularly 0.3 μ m is above especially more than 0.2 μ m) 50/below mL.
It should be noted that, the mensuration of the particle number in this organometallic compound solution is used scattering of light formula particle collector.
If the number of the particle more than 0.5 μ m of the particle diameter in organometallic compound solution exceedes 50/mL, long-term storing stability is poor.The number of particle more than the particle diameter 0.5 μ m in this organometallic compound solution is more few better, be particularly preferably 30/below mL.
The method that organometallic compound solution after processing modulation is above-mentioned particle number is not particularly limited, for example, can enumerate following method.As the 1st method, there is the membrane filter that uses 0.2 commercially available μ m aperture, carry out the filtration method of positive delivery with syringe.As the 2nd method, there is commercially available 0.05 membrane filter in μ m aperture and the pressure filtration method of pressurized tank of having combined.As the 3rd method, there is the strainer that uses in above-mentioned the 2nd method and the circulating filtration method of solution circulated groove of having combined.
Any method is all because of solution positive delivery pressure, the particle capture rate difference of strainer.Conventionally the lower catch rate of known pressure is higher, and particularly the 1st method, the 2nd method, in order to realize the condition of the number that makes particle more than particle diameter 0.5 μ m below 50, preferably makes solution pass through very lentamente strainer with low pressure.
The Strong dielectric film formation composition of the application of the invention, can form easily to take in the a kind of complex metal oxides A that is selected from PLZT, PZT and PT to mix and comprise the Strong dielectric film that is selected from the mixing complex metal oxides form that the one kind or two or more composite oxides B of P (phosphorus), Si, Ce and Bi obtains.
In order to use Strong dielectric film formation composition of the present invention to form Strong dielectric film, above-mentioned composition is coated to heat resistant substrate by coating methods such as spin-coating method, dip coated method, LSMCD (Liquid Source Misted Chemical Deposition) methods, be dried (pre-fired) and main burning till.
As the concrete example of the heat resistant substrate using, can enumerate in substrate skin section and use single crystalline Si, polycrystalline Si, Pt, Pt (the superiors)/Ti, Pt (the superiors)/Ta, Ru, RuO 2, Ru (the superiors)/RuO 2, RuO 2(the superiors)/Ru, Ir, IrO 2, Ir (the superiors)/IrO 2, Pt (the superiors)/Ir, Pt (the superiors)/IrO 2, SrRuO 3or (La xsr (1-x)) CoO 3deng the substrate of perovskite typed electroconductive oxide etc., but be not limited thereto.
It should be noted that, by 1 coating cannot obtain desirable thickness time, be repeatedly repeatedly coated with, after dry operation, lead and burn till.Herein, desirable thickness refers to the thickness of the Strong dielectric film obtaining after main burning till, when the film capacitor purposes of high capacity density, and the scope that the thickness of the Strong dielectric film after main burning till is 50～500nm.
In addition, pre-fired is for carrying out except making it be converted into composite oxides organometallic compound or organic compound thermolysis or hydrolysis in desolventizing, so in air, in oxidation atmosphere or carry out in containing water vapor atmosphere.Even heat in air, be hydrolyzed required moisture and fully guaranteed because of airborne moisture.This heating can be for implementing except the low-temperature heat of desolventizing with for 2 stages of heat of decomposing organometallic compound or organic compound.
Main burning till is to burn till the operation that makes its crystallization at the temperature of the film for pre-fired is obtained more than crystallized temperature, obtains thus Strong dielectric film.The atmosphere of burning till of this crystallization step is preferably O 2, N 2, Ar, N 2o or H 2deng or their mixed gas etc.
When composite oxides B contains P (phosphorus), pre-fired was carried out about 1～30 minute at 150～550 DEG C, and main burning till at 450～800 DEG C carried out about 1～10 minute.Master burns till also and can be undertaken by instant heating processing (RTA processing).Processed and led while burning till by RTA, this heat-up rate is preferably 10～100 DEG C/sec.
Composite oxides B contains while being selected from Si, Ce and Bi one kind or two or more, and pre-fired was carried out about 5～10 minutes at 150～550 DEG C, and main burning till at 450～800 DEG C carried out about 1～60 minute.Master burns till also and can be undertaken by instant heating processing (RTA processing).Processed and led while burning till by RTA, its heat-up rate is preferably 10～100 DEG C/sec.
When composite oxides B contains P (phosphorus), the Strong dielectric film of the present invention forming is thus that balance has improved that stray current reduces well and dielectric voltage withstand improves the film of two characteristics, as the fundamental characteristics excellence of electrical condenser, be applicable to the film capacitor purposes of high capacity density.In addition, Strong dielectric film of the present invention is also excellent as the fundamental characteristics of IPD.
When composite oxides B contains Si, the Strong dielectric film of the present invention forming thus can obtain the stray current density lower than existing Strong dielectric film and, high dielectric voltage withstand, so be applicable to film capacitor purposes.Therefore,, while being with the stray current density of existing Strong dielectric film same degree, further filming, obtains higher capacity density, as the fundamental characteristics excellence of electrical condenser.Also have and can reduce other advantages that starting material use by filming.In addition, Strong dielectric film of the present invention is also excellent as the fundamental characteristics of IPD.
When composite oxides B contains Ce, the Strong dielectric film of the present invention forming thus have with the relative permittivity of existing Strong dielectric film same degree and, can obtain low-leakage current density, so be applicable to the film capacitor purposes of high capacity density.Therefore,, while being with the stray current density of existing Strong dielectric film same degree, further filming, can obtain higher capacity density, as the fundamental characteristics excellence of electrical condenser.In addition, by filming, also have and can reduce other advantages that starting material use.In addition, Strong dielectric film of the present invention is also excellent as the fundamental characteristics of IPD.
When composite oxides B contains Bi, the Strong dielectric film of the present invention forming thus becomes the film that has significantly improved relative permittivity compared with existing Strong dielectric film, as the fundamental characteristics excellence of electrical condenser, be applicable to the film capacitor purposes of high capacity density.In addition, Strong dielectric film of the present invention is also excellent as the fundamental characteristics of IPD.
In addition, the Strong dielectric film of the 1st group can be used as the constituent material in the complex electronic device of film capacitor, electrical condenser, IPD, DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer.Wherein particularly also can be for the material corresponding to the above frequency band of 100MHz.
[the 2nd group]
Strong dielectric film formation in the 2nd group of the present invention is the composition that is used to form the a kind of Strong dielectric film that is selected from PLZT, PZT and PT with composition.The Strong dielectric film that uses said composition to form is to take in general formula (1): (Pb xla y) (Zr zti (1-z)) O 3in the complex metal oxides A that (0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9 in formula (1)) represents, mix to comprise and be selected from the mixing complex metal oxides form that the one kind or two or more composite oxides B (complex metal oxides) of Sn, Sm, Nd and Y (yttrium) obtains.It should be noted that, y ≠ 0 of above-mentioned formula (1) and z ≠ 0 o'clock are PLZT, and y=0 and z ≠ 0 o'clock are PZT, are PT when y=0 and z=0.
When composite oxides B contains Sn, said composition comprise raw material for forming complex metal oxides A and for the raw material that forms composite oxides B (complex metal oxides) taking can provide the above-mentioned general formula atoms metal that (1) represents ratio ratio and, the mol ratio B/A of composite oxides B (complex metal oxides) and complex metal oxides A in the scope of 0.003≤B/A≤0.05, be wherein particularly preferably ground, 0.006≤B/A≤0.04 and be dissolved in the organometallic compound solution of organic solvent.As long as in above-mentioned scope, just can significantly improve relative permittivity compared with existing Strong dielectric film.It should be noted that, when not enough lower value or while exceeding higher limit, obtain not having when not adding tin the result of large difference, be not suitable for the film capacitor purposes of high capacity density.
Composite oxides B contains while being selected from Sm, Nd and Y (yttrium) one kind or two or more, said composition comprise raw material for forming complex metal oxides A and for the raw material that forms composite oxides B (complex metal oxides) taking can provide the above-mentioned general formula atoms metal that (1) represents ratio ratio and, the mol ratio B/A of composite oxides B and complex metal oxides A in the scope of 0.005≤B/A < 0.03, be wherein particularly preferably ground, 0.005≤B/A≤0.02 and be dissolved in the organometallic compound solution of organic solvent.As long as in above-mentioned scope, just can significantly improve relative permittivity compared with existing Strong dielectric film.It should be noted that, not enough lower value or while exceeding higher limit, obtains and does not add the result that there is no large difference while being selected from samarium, neodymium and yttrium one kind or two or more, is not suitable for the film capacitor purposes of high capacity density.
In addition, comprise while being selected from Sn, Sm, Nd and Y (yttrium) one kind or two or more in composite oxides B, composite oxides B is complex metal oxides.
Complex metal oxides A with raw material and composite oxides B (complex metal oxides) raw material be preferably organic group via its oxygen or nitrogen atom bonding the compound on each metallic element of Pb, La, Zr, Ti, Sn, Sm, Nd and Y (yttrium).For example can enumerate and be selected from the one kind or two or more of metal alkoxide, metal glycol coordination compound, metal triol coordination compound, metal carboxylate, metal beta-diketon coordination compound, metal beta-diketo-ester coordination compound, metal β-imino-ketone coordination compound and metal amino coordination compound.Particularly preferred compound is metal alkoxide, its partial hydrolystate, organic acid salt.
Wherein, as Pb compound, La compound, can enumerate the alkoxide such as organic acid salt, plumbous diiso propoxide such as acetate (lead acetate, lanthanum acetate).As Sn compound, can enumerate the alkoxide such as organic acid salt, four propyl carbinol tin, ethanol tin such as acetate (tin acetate), nitrate (nitric acid tin), stannous octoate.
As Sm compound, can enumerate the metal beta-diketon coordination compoundes such as alkoxide, tri acetylacetonato samarium such as the organic acid salt such as 2-ethylhexoate (2 ethyl hexanoic acid samarium), 2 Ethylbutanoic acid salt (2 Ethylbutanoic acid samarium), four propyl carbinol samariums, ethanol samarium.
As Nd compound, can enumerate the metal beta-diketon coordination compoundes such as alkoxide, tri acetylacetonato neodymium such as the organic acid salt such as 2-ethylhexoate (2 ethyl hexanoic acid neodymium), 2 Ethylbutanoic acid salt (2 Ethylbutanoic acid neodymium), four propyl carbinol neodymiums, ethanol neodymium.
As Y (yttrium) compound, can enumerate the metal beta-diketon coordination compoundes such as alkoxide, tri acetylacetonato yttrium such as the organic acid salt such as 2-ethylhexoate (2 ethyl hexanoic acid yttrium), 2 Ethylbutanoic acid salt (2 Ethylbutanoic acid yttrium), three propyl carbinol yttriums, ethanol yttrium.
As Ti compound, can enumerate the alkoxide such as titanium tetraethoxide, titanium tetraisopropylate, four butanols titaniums, dimethoxy diisopropanol titanium.
As Zr compound, the preferably alcohol salt same with above-mentioned Ti compound.Metal alkoxide can directly use, but decomposes in order to promote, can use its partial hydrolystate.
In order to modulate Strong dielectric film formation composition of the present invention, by above-mentioned raw materials with the ratio solvent that is equivalent to desirable Strong dielectric film composition in suitable solvent, modulation is applicable to the concentration of coating.
Strong dielectric film used herein forms and suitably determines corresponding to the raw material of use with the solvent of composition, conventionally can use carboxylic acid, alcohol, ester, ketone (such as acetone, methyl ethyl ketone), ethers (such as dimethyl ether, Anaesthetie Ether), naphthenic (such as hexanaphthene, hexalin), the fragrant same clan (such as benzene,toluene,xylene), in addition tetrahydrofuran (THF) etc. or their mixed solvent of more than two kinds.
As carboxylic acid, particularly, preferably use butanic acid, α-methyl butyric acid, isovaleric acid, 2 Ethylbutanoic acid, 2,2-acid dimethyl, 3,3-acid dimethyl, 2,3-acid dimethyl, 3 methylvaleric acid, 4-methylvaleric acid, 2-ethyl valeric acid, 3-ethyl valeric acid, 2,2-dimethyl valeric acid, 3,3-dimethyl valeric acid, 2,3-dimethyl valeric acid, 2 ethyl hexanoic acid, 3-thylhexoic acid.
In addition, as ester, preferably use ethyl acetate, propyl acetate, n-butyl acetate, sec-butyl acetate, tert.-butyl acetate, isobutyl acetate, n-amyl acetate, sec-amyl acetate, tert.-amyl acetate, Isoamyl Acetate FCC, as alcohol, preferably use 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, isobutyl alcohol, 1-amylalcohol, 2-amylalcohol, 2-methyl-2-amylalcohol, 2-methyl cellosolve.
It should be noted that, Strong dielectric film formation is preferably 0.1～20 % by weight left and right by the total concn of the organometallic compound in the organometallic compound solution of composition in metal oxide conversion amount.
In this organometallic compound solution, can add as required beta-diketon class (for example methyl ethyl diketone of 0.2～3 left and right in (stabilization agent molecule number)/(atoms metal number), seven fluorine butyryl radicals valeryl methane, two valeryl methane, trifluoroacetylacetone, benzoyl acetone etc.), beta-keto acid class (for example etheric acid, propionyl acetic acid, benzoyl acetic acid etc.), 'beta '-ketoester class (the methyl esters of for example above-mentioned ketone acid, propyl ester, the lower alkyl esters classes such as butyl ester), hydroxyl acids (for example lactic acid, oxyacetic acid, alpha-hydroxybutyric acid, Whitfield's ointment etc.), the lower alkyl esters class of above-mentioned alcohol acid, quinones (for example diacetone alcohol, acetoin etc.), glycol, triol, high carboxylic acid, alkanol amine (for example diethanolamine, trolamine, monoethanolamine), polyamines etc. are as stabilization agent.
In the present invention, preferably by the organometallic compound solution of above-mentioned modulation by filtration treatment etc. except degranulation, the every 1mL solution of number that obtains the particle of particle diameter 0.5 μ m above (particularly 0.3 μ m is above especially more than 0.2 μ m) be 50/below mL.
It should be noted that, use scattering of light formula particle collector in order to measure the number of the particle in this organometallic compound solution.
If the number of the particle more than 0.5 μ m of the particle diameter in organometallic compound solution exceedes 50/mL, long-term storing stability is poor.The number of particle more than the particle diameter 0.5 μ m in this organometallic compound solution is more few better, be particularly preferably 30/below mL.
The method that organometallic compound solution after processing modulation is above-mentioned particle number is not particularly limited, for example, can enumerate following method.As the 1st method, there is the membrane filter that uses 0.2 commercially available μ m aperture, carry out the filtration method of positive delivery with syringe.As the 2nd method, there is commercially available 0.05 membrane filter in μ m aperture and the pressure filtration method of pressurized tank of having combined.As the 3rd method, there is the strainer that uses in above-mentioned the 2nd method and the circulating filtration method of solution circulated groove of having combined.
Any method is all because of the particle capture rate difference of solution positive delivery pressure strainer.Conventionally the lower catch rate of known pressure is higher, and particularly the 1st method, the 2nd method, in order to realize the condition of the number that makes particle more than particle diameter 0.5 μ m below 50, preferably makes solution pass through very lentamente strainer with low pressure.
The Strong dielectric film formation composition of the application of the invention, can form easily to take in the a kind of complex metal oxides A that is selected from PLZT, PZT and PT to mix and comprise the Strong dielectric film that is selected from the mixing complex metal oxides form that the one kind or two or more composite oxides B (complex metal oxides) of Sn, Sm, Nd and Y (yttrium) obtains.
In order to use Strong dielectric film formation composition of the present invention to form Strong dielectric film, above-mentioned composition is coated to heat resistant substrate by coating methods such as spin-coating method, dip coated method, LSMCD (Liquid Source MistedChemical Deposition) methods, be dried (pre-fired) and main burning till.
As the concrete example of the heat resistant substrate using, can enumerate in substrate skin section and use single crystalline Si, polycrystalline Si, Pt, Pt (the superiors)/Ti, Pt (the superiors)/Ta, Ru, RuO 2, Ru (the superiors)/RuO 2, RuO 2(the superiors)/Ru, Ir, IrO 2, Ir (the superiors)/IrO 2, Pt (the superiors)/Ir, Pt (the superiors)/IrO 2, SrRuO 3or (La xsr (1-x)) CoO 3deng the substrate of perovskite typed electroconductive oxide etc., but be not limited thereto.
It should be noted that, by 1 coating cannot obtain desirable thickness time, be repeatedly repeatedly coated with, after dry operation, lead and burn till.Herein, desirable thickness refers to the thickness of the Strong dielectric film obtaining after main burning till, when the film capacitor purposes of high capacity density, and the scope that the thickness of the Strong dielectric film after main burning till is 50～500nm.
In addition, pre-fired is for carrying out except making it be converted into composite oxides organometallic compound thermolysis or hydrolysis in desolventizing, so in air, in oxidation atmosphere or carry out in containing water vapor atmosphere.Even heat, be hydrolyzed required moisture also because airborne moisture is fully guaranteed in air.This heating also can be by the low-temperature heat for except desolventizing with for decomposing the heat 2 stages enforcement of organometallic compound.
Main burning till is to burn till the operation that makes its crystallization at the temperature of the film for pre-fired is obtained more than crystallized temperature, obtains thus Strong dielectric film.The atmosphere of burning till of this crystallization step is preferably O 2, N 2, Ar, N 2o or H 2deng or their mixed gas etc.
When composite oxides B contains Sn, pre-fired was carried out about 1～30 minute at 150～550 DEG C, and main burning till at 450～800 DEG C carried out about 1～10 minute.Master burns till also and can be undertaken by instant heating processing (RTA processing).Processed and led while burning till by RTA, its heat-up rate is preferably 10～100 DEG C/sec.
Composite oxides B contains while being selected from Sm, Nd and Y (yttrium) one kind or two or more, and pre-fired was carried out about 5～10 minutes at 150～550 DEG C, and main burning till at 450～800 DEG C carried out about 1～60 minute.Master burns till also and can be undertaken by instant heating processing (RTA processing).Processed and led while burning till by RTA, its heat-up rate is preferably 10～100 DEG C/sec.
The composite oxides B forming thus contains the one kind or two or more Strong dielectric film of the present invention that is selected from Sn, Sm, Nd and Y (yttrium) becomes the film that has significantly improved relative permittivity compared with existing Strong dielectric film, as the fundamental characteristics excellence of electrical condenser, be applicable to the film capacitor purposes of high capacity density.In addition, Strong dielectric film of the present invention is also excellent as the fundamental characteristics of IPD.
In addition, the Strong dielectric film in the 2nd group of the present invention can be used as the constituent material in the complex electronic device of film capacitor, electrical condenser, IPD, DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer.Wherein, particularly also can be for the material corresponding to the above frequency band of 100MHz.
[the 3rd group]
The Strong dielectric film formation of the 3rd group is the composition that is used to form the a kind of Strong dielectric film that is selected from PLZT, PZT and PT with composition.The Strong dielectric film that uses said composition to form is taked in general formula (1): (Pb xla y) (Zr zti (1-z)) O 3in the complex metal oxides A that (0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9 in formula (1)) represents, mix general formula (2) C nh 2n+1that COOH (wherein, 3≤n≤7) represents and, coordination can take complex metal oxides form structure, that carboxylic acid B obtains of following formula (3) on above-mentioned metal time.
[changing 2]
Wherein, in formula (3), meeting above-mentioned general formula (2) C nh 2n+1in the scope of the n of COOH, R1, R2, R3, R4, R5, R6 represent hydrogen, methyl or ethyl, and M represents Pb, La, Zr or Ti, and m represents the valence mumber of M.
It should be noted that, y ≠ 0 of above-mentioned formula (1) and z ≠ 0 o'clock are PLZT, and y=0 and z ≠ 0 o'clock are PZT, are PT when y=0 and z=0.Said composition comprise raw material for forming complex metal oxides A and carboxylic acid B taking the mol ratio B/A of carboxylic acid B and complex metal oxides A in the scope of 0 < B/A < 0.2, be wherein preferably 0.001≤B/A≤0.1, more preferably 0.03≤B/A≤0.1 and then the mode that is particularly preferably 0.05≤B/A≤0.1 and be dissolved in the organometallic compound solution of organic solvent.
By mixed carboxylic acid B in above-mentioned scope, the carboxylic acid (false carboxylate salt) of coordination on metallic element structurally becomes six-ring by the effect of hydrogen bond, the carbon bond of realizing ideal at low temperatures thus decomposes (for example can enumerate paragraph [0023], AllenW.Apblett etc., the Mat.Res.Soc.Symp.Proc.Vol.271pp.77 etc. of Unexamined Patent 9-52713 communique), so can realize low temperature crystallization, fully carry out crystal grain-growth while burning till.Think that thus relative permittivity improves.
In addition, think and be present in substrate interface by forming the three-dimensional coordination of the six-ring carboxylic acid on loose metallic element, pre-burning, suppress nucleus while burning till and generate.So the generation density of nucleus diminishes, compared with generating with the nucleus of substrate interface, the crystalline growth starting from substrate interface is more preponderated, and fully carries out crystal grain-growth while burning till.In view of above-mentioned reason, think that relative permittivity improves.
Therefore the Strong dielectric film that, uses Strong dielectric film formation composition of the present invention to form can significantly improve relative permittivity compared with existing Strong dielectric film.It should be noted that, when not enough lower value or while exceeding higher limit, there is no the result of large difference compared with obtaining when not adding carboxylic acid B, be not suitable for the film capacitor purposes of high capacity density.
Complex metal oxides A with the preferred organic group of raw material via its oxygen or nitrogen atom bonding the compound on each metallic element of Pb, La, Zr and Ti.For example can enumerate and be selected from the one kind or two or more of metal alkoxide, metal glycol coordination compound, metal triol coordination compound, metal carboxylate, metal beta-diketon coordination compound, metal beta-diketo-ester coordination compound, metal β-imino-ketone coordination compound and metal amino coordination compound.Particularly preferred compound is metal alkoxide, its partial hydrolystate, organic acid salt.Wherein, as Pb compound, La compound, can enumerate the alkoxide such as organic acid salt, diisopropanol lead such as acetate (lead acetate, lanthanum acetate).As Ti compound, can enumerate the alkoxide such as titanium tetraethoxide, titanium tetraisopropylate, four butanols titaniums, dimethoxy diisopropanol titanium.As Zr compound, the preferably alcohol salt same with above-mentioned Ti compound.Metal alkoxide can directly use, but decomposes in order to promote, can use its partial hydrolystate.
In addition, Strong dielectric film formation of the present invention can be enumerated the compound shown in following table 1 with the carboxylic acid B that can use in composition.
[table 1]
In order to modulate Strong dielectric film formation composition of the present invention, by above-mentioned raw materials with the ratio solvent that is equivalent to desirable Strong dielectric film composition in suitable solvent, modulation is applicable to the concentration of coating.
Strong dielectric film used herein forms and suitably determines corresponding to the raw material of use with the solvent of composition, conventionally can use alcohol, ester, ketone (such as acetone, methyl ethyl ketone), ethers (such as dimethyl ether, Anaesthetie Ether), naphthenic (such as hexanaphthene, hexalin), the fragrant same clan (such as benzene,toluene,xylene), in addition tetrahydrofuran (THF) etc. or their mixed solvent of more than two kinds.
As ester, preferably use ethyl acetate, propyl acetate, n-butyl acetate, sec-butyl acetate, tert.-butyl acetate, isobutyl acetate, n-amyl acetate, sec-amyl acetate, tert.-amyl acetate, Isoamyl Acetate FCC, as alcohol, preferably use 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, isobutyl alcohol, 1-amylalcohol, 2-amylalcohol, 2-methyl-2-amylalcohol, 2-methyl cellosolve.
It should be noted that, Strong dielectric film formation is preferably 0.1～20 quality % left and right by the total concn of the organometallic compound in the organometallic compound solution of composition in metal oxide conversion amount.
In this organometallic compound solution, add as required beta-diketon class (for example methyl ethyl diketone of 0.2～3 left and right in (stabilization agent molecule number)/(atoms metal number), seven fluorine butyryl radicals valeryl methane, two valeryl methane, trifluoroacetylacetone, benzoyl acetone etc.), beta-keto acid class (for example etheric acid, propionyl acetic acid, benzoyl acetic acid etc.), 'beta '-ketoester class (the methyl esters of for example above-mentioned ketone acid, propyl ester, the lower alkyl esters classes such as butyl ester), hydroxyl acids (for example lactic acid, oxyacetic acid, alpha-hydroxybutyric acid, Whitfield's ointment etc.), the lower alkyl esters class of above-mentioned alcohol acid, quinones (for example diacetone alcohol, acetoin etc.), glycol, triol, alkanol amine (for example diethanolamine, trolamine, monoethanolamine), polyamines etc. are as stabilization agent.
In the present invention, preferably by the organometallic compound solution of above-mentioned modulation by filtration treatment etc. except degranulation, make particle diameter 0.5 μ m above (particularly 0.3 μ m is above especially more than 0.2 μ m) particle the every 1mL solution of number 50/below mL.
If the number of the particle more than 0.5 μ m of the particle diameter in organometallic compound solution exceedes 50/mL, long-term storing stability is poor.The number of particle more than the particle diameter 0.5 μ m in this organometallic compound solution is more few better, be particularly preferably 30/below mL.
The method that organometallic compound solution after processing modulation is above-mentioned particle number is not particularly limited, for example, can enumerate following method.As the 1st method, there is the membrane filter that uses 0.2 commercially available μ m aperture, carry out the filtration method of positive delivery with syringe.As the 2nd method, there is commercially available 0.05 membrane filter in μ m aperture and the pressure filtration method of pressurized tank of having combined.As the 3rd method, there is the strainer that uses in above-mentioned the 2nd method and the circulating filtration method of solution circulated groove of having combined.
Any method is all because of the particle capture rate difference of solution positive delivery pressure strainer.Conventionally the lower catch rate of known pressure is higher, and particularly the 1st method, the 2nd method, in order to realize the condition of the number that makes particle more than particle diameter 0.5 μ m below 50, preferably makes solution pass through very lentamente strainer with low pressure.
The Strong dielectric film formation composition of the application of the invention, can form the Strong dielectric film of the form of taking the complex metal oxides A of a kind that is selected from PLZT, PZT and PT easily.
In order to use Strong dielectric film formation composition of the present invention to form Strong dielectric film, above-mentioned composition is coated to heat resistant substrate by coating methods such as spin-coating method, dip coated method, LSMCD (Liquid Source MistedChemical Deposition) methods, be dried (pre-fired) and main burning till.
As the concrete example of the heat resistant substrate using, can enumerate in substrate skin section and use single crystalline Si, polycrystalline Si, Pt, Pt (the superiors)/Ti, Pt (the superiors)/Ta, Ru, RuO 2, Ru (the superiors)/RuO 2, RuO 2(the superiors)/Ru, Ir, IrO 2, Ir (the superiors)/IrO 2, Pt (the superiors)/Ir, Pt (the superiors)/IrO 2, SrRuO 3or (La xsr (1-x)) CoO 3deng the substrate of perovskite typed electroconductive oxide etc., but be not limited thereto.
It should be noted that, by 1 coating cannot obtain desirable thickness time, be repeatedly repeatedly coated with, after dry operation, lead and burn till.Herein, desirable thickness refers to the thickness of the Strong dielectric film obtaining after main burning till, when the film capacitor purposes of high capacity density, and the scope that the thickness of the Strong dielectric film after main burning till is 50～500nm.
In addition, pre-fired is for carrying out except making it be converted into composite oxides organometallic compound thermolysis or hydrolysis in desolventizing, so in air, in oxidation atmosphere or carry out in containing water vapor atmosphere.Even heat, be hydrolyzed required moisture also because airborne moisture is fully guaranteed in air.This heating can be by the low-temperature heat for except desolventizing with for decomposing the heat 2 stages enforcement of organometallic compound.
Main burning till is to burn till the operation that makes its crystallization at the temperature of the film for pre-fired is obtained more than crystallized temperature, obtains thus Strong dielectric film.The atmosphere of burning till of this crystallization step is preferably O 2, N 2, Ar, N 2o or H 2deng or their mixed gas etc.
Pre-fired was carried out about 5～10 minutes at 150～550 DEG C, and main burning till at 450～800 DEG C carried out about 1～60 minute.Master burns till also and can be undertaken by instant heating processing (RTA processing).Processed and led while burning till by RTA, its heat-up rate is preferably 10～100 DEG C/sec.
The Strong dielectric film of the 3rd group forming thus becomes the film that has significantly improved relative permittivity compared with existing Strong dielectric film, as the fundamental characteristics excellence of electrical condenser, is applicable to the film capacitor purposes of high capacity density.In addition, Strong dielectric film of the present invention is also excellent as the fundamental characteristics of IPD.
In addition, the Strong dielectric film of the 3rd group can be used as the constituent material in the complex electronic device of film capacitor, electrical condenser, IPD, DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer.Wherein particularly also can be for the material corresponding to the above frequency band of 100MHz.
Embodiment
[the 1st group]
Below embodiments of the invention A-1～embodiment A-29 and Comparative examples A-1～Comparative examples A-8 are together described in detail.
It should be noted that, in following embodiment A-1～embodiment A-29 and Comparative examples A-1～Comparative examples A-8, use following substances as raw material.
Pb compound: lead acetate 3 hydrates
La compound: lanthanum acetate 1.5 hydrates
Zr compound: four zirconium tert-butoxide
Ti compound: titanium tetraisopropylate
P (phosphorus) compound: three Virahol P (phosphorus), tricresyl phosphate ethyl ester
< embodiment A-1～embodiment A-29, Comparative examples A-1～Comparative examples A-8>
As organic solvent, use the 2-methyl cellosolve that has fully carried out processed, the organometallic compound (Pb, La compound etc.) of organic acid salt form is dissolved in wherein, remove crystal water by component distillation.Then, in the solution obtaining, add organometallic compound or the organic compound (Zr, Ti, P (phosphorus) compound etc.) of alkoxide form, make its dissolving, for solution-stabilizedization, add methyl ethyl diketone or the diethanolamine of 2 times moles with respect to alkoxide, make PZT be the interpolation element kind shown in following table 2 or table 3 and addition modulate the total concn of organometallic compound with the film formation solution of metal oxide conversion densitometer approximately 10 % by weight.
Use each solution, utilize CSD method to carry out the formation of film by following method.
, by spin-coating method under 500rpm 3 seconds, then under the condition in 15 seconds, each solution coat has been formed by sputter on surface on 6 inches of silicon substrates of Pt film under 3000rpm.
Then, use hot plate, at 350 DEG C, heat and within 10 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere or dry air atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 300nm.
Then, use metal mask, the Pt upper electrode of making approximately 250 μ m on surface by sputter, applies volts DS between the Pt lower electrode under Strong dielectric film, evaluates I-V characteristic (voltage-dependent of stray current density and dielectric voltage withstand).It should be noted that, the mensuration of I-V characteristic is used the 236SMU processed of Keithley company, under the condition of Bias step 0.5V, Delay time0.1sec, 23 DEG C of Temperature, Hygrometry 50 ± 10%, measures.In addition, the definition of " dielectric voltage withstand " is that stray current density exceedes 1A/cm 21 before the voltage of Biasstep.The results are shown in following table 2, table 3 and Fig. 1～Fig. 4.
[table 2]
[table 3]
From table 2 and Fig. 1～Fig. 4, with not containing compared with the Strong dielectric film of Comparative examples A-1 of P (phosphorus), added in the Strong dielectric film of embodiment A-1～embodiment A-5 of P (phosphorus), when having confirmed the reduction of stray current density, dielectric voltage withstand improves.
In addition, more also show same tendency containing the Strong dielectric film of Comparative examples A-2 of La, Comparative examples A-3 with containing La time containing the Strong dielectric film of embodiment A-11～embodiment A-13 of P (phosphorus).
If confirmed to add Sn by Comparative examples A-1 and Comparative examples A-4, stray current density increases, but as shown in embodiment A-6～embodiment A-8, if the P that coexists (phosphorus) has similarly confirmed the effect that when stray current density reduces, dielectric voltage withstand improves.
In addition, by the result of the Strong dielectric film of embodiment A-6～embodiment A-10, even with coexist other compositions such as Sn or Si of 1% left and right of P (phosphorus) simultaneously, also can confirm the good result of P (phosphorus), confirm that P (phosphorus) is the interpolation element of very influencing characteristic.
In addition, from the result of the Strong dielectric film of embodiment A-14～embodiment A-19, embodiment A-20～embodiment A-25 and Comparative examples A-5, Comparative examples A-6, with add P (phosphorus) compound form, stabilization agent kind, to burn till atmosphere irrelevant, can realize that stray current density reduces and dielectric voltage withstand raising simultaneously.
And then, from the result of the Strong dielectric film of embodiment A-26～embodiment A-29 and Comparative examples A-7, Comparative examples A-8, even if also can confirm same good tendency under the coexisting of La.
From the above results, the Strong dielectric film of embodiment A-1～embodiment A-29 has sews withstand voltage and effect dielectric voltage withstand excellence, can thin layer, so can realize high capacity density.
The Strong dielectric film obtaining in embodiment A-1～embodiment A-29, as the fundamental characteristics excellence of electrical condenser, can be used in the purposes of the film capacitor of high capacity density.
Below embodiments of the invention B-1～Embodiment B-75 are together described in detail with comparative example B-1～comparative example B-6.
< Embodiment B-1～Embodiment B-5>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various silicon compounds (2 ethyl hexanoic acid silicon, 2 Ethylbutanoic acid silicon, tetraethoxide silicon, four propyl carbinol silicon, four (methyl ethyl diketone) silicon) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< Embodiment B-6～Embodiment B-10>
In sol gel solution, add the various silicon compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment B-1～Embodiment B-5.
< Embodiment B-11～Embodiment B-15>
In sol gel solution, add the various silicon compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment B-1～Embodiment B-5.
< Embodiment B-16～Embodiment B-20>
In sol gel solution, add the various silicon compounds of counting 5.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment B-1～Embodiment B-5.
< Embodiment B-21～Embodiment B-25>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and lanthanum acetate 1.5 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain containing the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound of the 10 quality % concentration of Pb/La/Zr/Ti=110/3/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various silicon compounds (2 ethyl hexanoic acid silicon, 2 Ethylbutanoic acid silicon, tetraethoxide silicon, four propyl carbinol silicon, four (methyl ethyl diketone) silicon) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< comparative example B-1>
In sol gel solution, do not add silicon compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment B-1～Embodiment B-5.
< comparative example B-2>
In sol gel solution, do not add silicon compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment B-21～Embodiment B-25.
< Embodiment B-26～Embodiment B-30>
First, in reaction vessel, add four zirconium-n-butylates and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various silicon compounds (2 ethyl hexanoic acid silicon, 2 Ethylbutanoic acid silicon, tetraethoxide silicon, four propyl carbinol silicon, four (methyl ethyl diketone) silicon) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< Embodiment B-31～Embodiment B-35>
In sol gel solution, add the various silicon compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment B-26～Embodiment B-30.
< Embodiment B-36～Embodiment B-40>
In sol gel solution, add the various silicon compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment B-26～Embodiment B-30.
< Embodiment B-41～Embodiment B-45>
In sol gel solution, add the various silicon compounds of counting 5.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment B-26～Embodiment B-30.
< Embodiment B-46～Embodiment B-50>
First, in reaction vessel, add four zirconium-n-butylates and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and lanthanum acetate 1.5 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain containing the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound of the 10 quality % concentration of Pb/La/Zr/Ti=110/3/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various silicon compounds (2 ethyl hexanoic acid silicon, 2 Ethylbutanoic acid silicon, tetraethoxide silicon, four propyl carbinol silicon, four (methyl ethyl diketone) silicon) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< comparative example B-3>
In sol gel solution, do not add silicon compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment B-26～30.
< comparative example B-4>
In sol gel solution, do not add silicon compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment B-46～50.
< Embodiment B-51～Embodiment B-55>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various silicon compounds (2 ethyl hexanoic acid silicon, 2 Ethylbutanoic acid silicon, tetraethoxide silicon, four propyl carbinol silicon, four (methyl ethyl diketone) silicon) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in dry air atmosphere, burn till the Strong dielectric film of formation thickness 270nm by the RTA (instant heating treatment unit) of 1 minute at 700 DEG C.
< Embodiment B-56～Embodiment B-60>
In sol gel solution, add the various silicon compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment B-51～Embodiment B-55.
< Embodiment B-61～Embodiment B-65>
In sol gel solution, add the various silicon compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment B-51～Embodiment B-55.
< Embodiment B-66～Embodiment B-70>
In sol gel solution, add the various silicon compounds of counting 5.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment B-51～Embodiment B-55.
< Embodiment B-71～Embodiment B-75>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and lanthanum acetate 1.5 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain containing the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound of the 10 quality % concentration of Pb/La/Zr/Ti=110/3/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various silicon compounds (2 ethyl hexanoic acid silicon, 2 Ethylbutanoic acid silicon, tetraethoxide silicon, four propyl carbinol silicon, four (methyl ethyl diketone) silicon) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in dry air atmosphere, burn till the Strong dielectric film of formation thickness 270nm by the RTA (instant heating treatment unit) of 1 minute at 700 DEG C.
< comparative example B-5>
In sol gel solution, do not add silicon compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment B-51～Embodiment B-55.
< comparative example B-6>
In sol gel solution, do not add silicon compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment B-71～Embodiment B-75.
< comparative evaluation >
For the formation obtaining in Embodiment B-1～Embodiment B-75 and comparative example B-1～comparative example B-6 the substrate of Strong dielectric film, use metal mask, make the Pt upper electrode of approximately 250 μ m by sputtering at surface, between the Pt lower electrode under Strong dielectric film, apply volts DS, evaluate I-V characteristic (voltage-dependent of stray current density and dielectric voltage withstand).Its result is shown in to following table 4～table 6.In addition, the I-V performance chart of Embodiment B-3, Embodiment B-8, Embodiment B-13, Embodiment B-18, Embodiment B-23 and comparative example B-1, comparative example B-2 is shown in Fig. 5～Figure 11.It should be noted that, in the mensuration of I-V characteristic, use the 236SMU processed of Keithley company, under the condition of Bias step 0.5V, Delay time 0.1sec, 23 DEG C of Temperature, Hygrometry 50 ± 10%, measure.In addition, the definition of " dielectric voltage withstand " is that stray current density exceedes 1A/cm 21 before the voltage of Bias step.It should be noted that, " > 99.5 " in table 4～table 6 represents the voltage determination limit of determinator.
[table 4]
[table 5]
[table 6]
From table 4～table 6 and Fig. 5～Figure 11, with not containing compared with the PZT Strong dielectric film of comparative example B-1, the comparative example B-3 of Si, comparative example B-5, add in the PZT Strong dielectric film of Embodiment B-1～Embodiment B-20, Embodiment B-26～Embodiment B-45, Embodiment B-51～Embodiment B-70 of Si, confirmed that dielectric voltage withstand improves when stray current density reduces.
In addition, even if relatively, containing the PLZT Strong dielectric film of comparative example B-2, the comparative example B-4 of La, comparative example B-6 with simultaneously containing the PLZT Strong dielectric film of Embodiment B-21～Embodiment B-25 of Si and La, Embodiment B-46～Embodiment B-50, Embodiment B-71～Embodiment B-75, also show same tendency.
Judge that by the above results the Strong dielectric film of Embodiment B-1～Embodiment B-75 has the effect of stray current density and dielectric voltage withstand excellence.In addition, the Strong dielectric film that makes Embodiment B-1～Embodiment B-75 is during with the level of the stray current density of the Strong dielectric film same degree of comparative example B-1～comparative example B-6, further filming, by filming, has advantages of and can obtain more high relative dielectric constant.In addition, also there is the raw-material advantage that can reduce use.
The Strong dielectric film obtaining in Embodiment B-1～Embodiment B-75 is as the fundamental characteristics excellence of electrical condenser, can be used in high-density, electrical condenser that high puncture of insulation is withstand voltage.
Describe embodiments of the invention C-1～Embodiment C-51 and comparative example C-1～comparative example C-6 below in detail.
< Embodiment C-1～Embodiment C-5>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various cerium compounds (2 ethyl hexanoic acid cerium, 2 Ethylbutanoic acid cerium, three ethanol ceriums, three propyl carbinol ceriums, tri acetylacetonato cerium) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< Embodiment C-6～Embodiment C-10>
In sol gel solution, add the various cerium compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-1～Embodiment C-5.
< Embodiment C-11～Embodiment C-15>
In sol gel solution, add the various cerium compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-1～Embodiment C-5.
< Embodiment C-16>
In sol gel solution, add and count the lanthanum compound (lanthanum acetate 1.5 hydrates) of 1.0mol% and the cerium compound (2 ethyl hexanoic acid cerium) of 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-1～Embodiment C-5.
< Embodiment C-17>
In sol gel solution, add and count the lanthanum compound (lanthanum acetate 1.5 hydrates) of 1.0mol% and the cerium compound (three ethanol ceriums) of 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-1～Embodiment C-5.
< comparative example C-1>
In sol gel solution, do not add cerium compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-1～Embodiment C-5.
< comparative example C-2>
In sol gel solution, do not add cerium compound, replace and add the lanthanum compound (lanthanum acetate 1.5 hydrates) of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-1～Embodiment C-5.
< Embodiment C-18～Embodiment C-22>
First, in reaction vessel, add four zirconium-n-butylates and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various cerium compounds (2 ethyl hexanoic acid cerium, 2 Ethylbutanoic acid cerium, three ethanol ceriums, three propyl carbinol ceriums, tri acetylacetonato cerium) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< Embodiment C-23～Embodiment C-27>
In sol gel solution, add the various cerium compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-18～Embodiment C-22.
< Embodiment C-28～Embodiment C-32>
In sol gel solution, add the various cerium compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-18～Embodiment C-22.
< Embodiment C-33>
In sol gel solution, add and count the lanthanum compound (lanthanum acetate 1.5 hydrates) of 1.0mol% and the cerium compound (2 ethyl hexanoic acid cerium) of 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-18～Embodiment C-22.
< Embodiment C-34>
In sol gel solution, add and count the lanthanum compound (lanthanum acetate 1.5 hydrates) of 1.0mol% and the cerium compound (three ethanol ceriums) of 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-18～Embodiment C-22.
< comparative example C-3>
In sol gel solution, do not add cerium compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-18～Embodiment C-22.
< comparative example C-4>
In sol gel solution, do not add cerium compound, replace and add the lanthanum compound (lanthanum acetate 1.5 hydrates) of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-18～Embodiment C-22.
< Embodiment C-35～Embodiment C-39>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various cerium compounds (2 ethyl hexanoic acid cerium, 2 Ethylbutanoic acid cerium, three ethanol ceriums, three propyl carbinol ceriums, tri acetylacetonato cerium) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in dry air atmosphere, burn till the Strong dielectric film of formation thickness 270nm by the RTA (instant heating treatment unit) of 1 minute at 700 DEG C.
< Embodiment C-40～Embodiment C-44>
In sol gel solution, add the various cerium compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-35～Embodiment C-39.
< Embodiment C-45～Embodiment C-49>
In sol gel solution, add the various cerium compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-35～Embodiment C-39.
< Embodiment C-50>
In sol gel solution, add and count the lanthanum compound (lanthanum acetate 1.5 hydrates) of 1.0mol% and the cerium compound (2 ethyl hexanoic acid cerium) of 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-35～Embodiment C-39.
< Embodiment C-51>
In sol gel solution, add and count the lanthanum compound (lanthanum acetate 1.5 hydrates) of 1.0mol% and the cerium compound (three ethanol ceriums) of 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-35～Embodiment C-39.
< comparative example C-5>
In sol gel solution, do not add cerium compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-35～Embodiment C-39.
< comparative example C-6>
In sol gel solution, do not add cerium compound, replace and add the lanthanum compound (lanthanum acetate 1.5 hydrates) of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with Embodiment C-35～Embodiment C-39.
< comparative evaluation >
For the formation obtaining in Embodiment C-1～Embodiment C-51 and comparative example C-1～comparative example C-6 the substrate of Strong dielectric film, use metal mask, make the Pt upper electrode of approximately 250 μ m by sputter on surface, between the Pt lower electrode under Strong dielectric film, apply volts DS, evaluate I-V characteristic (voltage-dependent of stray current density).In addition, between the Pt lower electrode under Strong dielectric film, under frequency 1kHz, in the scope inner evaluation C-V of-5～5V characteristic (voltage-dependent of electrostatic capacity), calculate relative permittivity ε r by the maximum value of electrostatic capacity.By its result respectively at following table 7～table 9.It should be noted that, the mensuration of I-V characteristic is used the 236SMU processed of Keithley company, under the condition of Bias step 0.5V, Delay time0.1sec, 23 DEG C of Temperature, Hygrometry 50 ± 10%, measures.In addition, the mensuration of C-V characteristic is used the 4284A precision processed LCR meter of Hewlett-Packard Corporation, under the condition of Biasstep 0.1V, Frequency 1kHz, Oscillation level 30mV, Delay time 0.2sec, 23 DEG C of Temperature, Hygrometry 50 ± 10%, measures.
[table 7]
[table 8]
[table 9]
From table 7～table 9, the Strong dielectric film that has added Embodiment C-1～Embodiment C-51 of Ce can obtain than the low stray current density of PZT Strong dielectric film that does not contain comparative example C-1～comparative example C-6 of Ce with the thin thickness in 270nm left and right.
In addition, with PLZT Strong dielectric film containing comparative example C-2, the comparative example C-4 of La, comparative example C-6 relatively in, in the time applying 5V, while applying 20V, all confirmed that stray current density reduces.
In addition, for electrostatic capacity and relative permittivity, if compared with the Strong dielectric film of the Strong dielectric film of Embodiment C-1～Embodiment C-51 and comparative example C-1～comparative example C-6, also observe the lower slightly example of numerical value, but be generally result in no way inferior, can be described as the numerical value obtaining no less than at present known Strong dielectric film.
But, the Strong dielectric film that makes Embodiment C-1～Embodiment C-51 is during with the level of the stray current density of the Strong dielectric film same degree of comparative example C-1～comparative example C-6, further filming, by filming, has advantages of and can obtain more high relative dielectric constant.
From the above results, the Strong dielectric film of Embodiment C-1～Embodiment C-51 does not make relative permittivity reduce, and has stray current density and reduces excellent effect, can filming, can realize high capacity density.
The Strong dielectric film obtaining in Embodiment C-1～Embodiment C-51 is as the fundamental characteristics excellence of electrical condenser, can be used in high-density, electrical condenser that high puncture of insulation is withstand voltage.
Describe embodiments of the invention D-1～embodiment D-75 and Comparative Example D-1～Comparative Example D-3 below in detail.
< embodiment D-1～embodiment D-5>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various bismuth compounds (2 ethyl hexanoic acid bismuth, 2 Ethylbutanoic acid bismuth, three Virahol bismuths, three tertiary amyl alcohol bismuths, four (methyl heptadione) bismuth) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< embodiment D-6～embodiment D-10>
In sol gel solution, add the various bismuth compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment D-1～embodiment D-5.
< embodiment D-11～embodiment D-15>
In sol gel solution, add the various bismuth compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment D-1～embodiment D-5.
< embodiment D-16～embodiment D-20>
In sol gel solution, add the various bismuth compounds of counting 5.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment D-1～embodiment D-5.
< embodiment D-21～embodiment D-25>
In sol gel solution, add the various bismuth compounds of counting 10.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment D-1～embodiment D-5.
< Comparative Example D-1>
In the sol gel solution of embodiment D-1, do not add bismuth compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment D-1～embodiment D-5.
< embodiment D-26～embodiment D-30>
First, in reaction vessel, add four zirconium-n-butylates and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion 222q as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various bismuth compounds (2 ethyl hexanoic acid bismuth, 2 Ethylbutanoic acid bismuth, three Virahol bismuths, three tertiary amyl alcohol bismuths, four (methyl heptadione) bismuth) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< embodiment D-31～embodiment D-35>
In sol gel solution, add the various bismuth compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment D-26～embodiment D-30.
< embodiment D-36～embodiment D-40>
In sol gel solution, add the various bismuth compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment D-26～embodiment D-30.
< embodiment D-41～embodiment D-45>
In sol gel solution, add the various bismuth compounds of counting 5.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment D-26～embodiment D-30.
< embodiment D-46～embodiment D-50>
In sol gel solution, add the various bismuth compounds of counting 10.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment D-26～30.
< Comparative Example D-2>
In the sol gel solution of embodiment D-26, do not add bismuth compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment D-26～embodiment D-30.
< embodiment D-51～embodiment D-55>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various bismuth compounds (2 ethyl hexanoic acid bismuth, 2 Ethylbutanoic acid bismuth, three Virahol bismuths, three tertiary amyl alcohol bismuths, four (methyl heptadione) bismuth) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in dry air atmosphere, burn till the Strong dielectric film of formation thickness 270nm by the RTA (instant heating treatment unit) of 1 minute at 700 DEG C.
< embodiment D-56～embodiment D-60>
In sol gel solution, add the various bismuth compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment D-51～embodiment D-55.
< embodiment D-61～embodiment D-65>
In sol gel solution, add the various bismuth compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment D-51～embodiment D-55.
< embodiment D-66～embodiment D-70>
In sol gel solution, add the various bismuth compounds of counting 5.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment D-51～embodiment D-55.
< embodiment D-71～embodiment D-75>
In sol gel solution, add the various bismuth compounds of counting 10.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment D-51～embodiment D-55.
< Comparative Example D-3>
In the sol gel solution of embodiment D-51, do not add bismuth compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment D-51～embodiment D-55.
< comparative evaluation >
For the formation obtaining in embodiment D-1～embodiment D-75 and Comparative Example D-1～Comparative Example D-3 substrate of Strong dielectric film, use metal mask, make the Pt upper electrode of approximately 250 μ m by sputtering at surface, between the Pt lower electrode under Strong dielectric film with frequency 1kHz in the scope inner evaluation C-V of-5～5V characteristic (voltage-dependent of electrostatic capacity), calculate relative permittivity ε r by the maximum value of electrostatic capacity.It should be noted that, the mensuration of C-V characteristic is used the 4284A precision processed LCR meter of Hewlett-Packard Corporation, under Bias step 0.1V, Frequency 1kHz, Oscillation level 30mV, Delay time 0.2sec, Temperature23 DEG C, the condition of Hygrometry 50 ± 10%, measures.The results are shown in following table 10～table 12.
[table 10]
[table 11]
[table 12]
From table 10～table 12, with not containing compared with the PZT Strong dielectric film of Comparative Example D-1～Comparative Example D-3 of Bi, added the Strong dielectric film of embodiment D-1～embodiment D-75 of 0.5%～10%Bi and confirmed high electrostatic capacity and high relative dielectric constant with the thin thickness in 270nm left and right.Judge that by this result the Strong dielectric film of embodiment D-1～embodiment D-75 is as the fundamental characteristics excellence of electrical condenser.
In addition, from the result of the Strong dielectric film of embodiment D-1～embodiment D-75 that the addition of Bi is changed, add embodiment D-16～embodiment D-20 of 5%, embodiment D-41～embodiment D-45, the result of embodiment D-66～embodiment D-70 is high especially, then, add embodiment D-11～embodiment D-15 of 3%, embodiment D-36～embodiment D-40, the result of embodiment D-61～embodiment D-65, add embodiment D-21～embodiment D-25 of 10%, embodiment D-46～embodiment D-50, the result of embodiment D-71～embodiment D-75, add embodiment D-6～embodiment D-10 of 1%, embodiment D-31～embodiment D-35, the result of embodiment D-56～embodiment D-60 is taken second place, add embodiment D-1～embodiment D-5 of 0.5%, embodiment D-26～embodiment D-30, the result of embodiment D-51～embodiment D-55 is low.
By this results verification there is the scope that can contribute to the suitable Bi addition that electrostatic capacity and relative permittivity ε r improve.
The Strong dielectric film obtaining in embodiment D-1～embodiment D-75, as the fundamental characteristics excellence of electrical condenser, can be used for the purposes of the film capacitor of high capacity density.
[the 2nd group]
Describe embodiments of the invention E-1～embodiment E-27 and Comparative Example E-1～Comparative Example E-8 below in detail.
It should be noted that, in following embodiment E-1～embodiment E-27 and Comparative Example E-1～Comparative Example E-8, use following substances as raw material.
Pb compound: lead acetate 3 hydrates
La compound: lanthanum acetate 1.5 hydrates
Zr compound: four zirconium tert-butoxide
Ti compound: titanium tetraisopropylate
Sn compound: tin acetate, stannous octoate, nitric acid tin, four propyl carbinol tin, ethanol tin
< embodiment E-1～embodiment E-27, Comparative Example E-1～Comparative Example E-8>
As organic solvent, use the 2-methyl cellosolve that has fully carried out processed, dissolve therein the organometallic compound (Pb, La, Sn compound etc.) of organic acid salt and nitrate form, remove crystal water by component distillation.Then, in the solution obtaining, add organometallic compound or the organic compound (Zr, Ti, Sn compound etc.) of alkoxide form, make its dissolving, for solution-stabilizedization, add methyl ethyl diketone or the diethanolamine of 2 times moles with respect to metal alkoxide, modulate the total concn of organometallic compound with the film formation solution of metal oxide conversion densitometer approximately 10 % by weight to reach the mode of the interpolation element kind shown in following table 13 or table 14 and addition in PZT.
Use each solution, utilize CSD method to carry out the formation of film by following method.
, under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be under the condition in 15 seconds, each solution coat have been formed by sputter on surface on 6 inches of silicon substrates of Pt film.
Then, use hot plate, at 350 DEG C, heat and within 10 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere or dry air atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 300nm.
Then, use metal mask, make the Pt upper electrode of approximately 250 μ m by sputtering at surface, between the Pt lower electrode under Strong dielectric film with frequency 1kHz in the scope inner evaluation C-V of-5～5V characteristic (voltage-dependent of electrostatic capacity), calculate relative permittivity ε r by the maximum value of electrostatic capacity.It should be noted that, the mensuration of C-V characteristic is used the 4284A precision processed LCR meter of Hewlett-Packard Corporation, under the condition of Bias step 0.1V, Frequency 1kHz, Oscillation level 30mV, Delay time 0.2sec, 23 DEG C of Temperature, Hygrometry50 ± 10%, measures.The results are shown in following table 13, table 14 and Figure 12.In addition, the C-V graphic representation of embodiment E-2, embodiment E-7 and Comparative Example E-1 is shown in Figure 13～Figure 15.
[table 13]
[table 14]
From table 13 and Figure 12, compared with the PLZT Strong dielectric film of not the PZT Strong dielectric film containing Comparative Example E-1 of Sn, Comparative Example E-2, add in the Strong dielectric film of embodiment E-1～embodiment E-9 of Sn, confirm high relative dielectric constant ε r.Judged that by this result the Strong dielectric film of embodiment E-1～embodiment E-9 is as the fundamental characteristics excellence of electrical condenser.
But the PZT Strong dielectric film that has added Comparative Example E-6 of 10%Sn is than the low result of PZT Strong dielectric film that does not contain Comparative Example E-1 of Sn.
In addition, from the result of Strong dielectric film of embodiment E-1～embodiment E-4, Comparative Example E-6 of addition that changes Sn, the result of having added 1% embodiment E-2 is high especially, then, the result of having added 3% embodiment E-3 is high, added 0.5% embodiment E-1 and added the result that the result of 5% embodiment E-4 of adding is basic identical degree, the result of having added 10% Comparative Example E-6 is low.By this results verification exist can contribute to relative permittivity ε r improve suitable Sn addition scope.
In addition, according to the result of the Strong dielectric film of embodiment E-5～embodiment E-8 and Comparative Example E-3～Comparative Example E-5, even also can confirm the good result of Sn with coexist other compositions such as Si or P of 1% left and right of Sn simultaneously.The relative permittivity ε r higher than other examples confirmed in particularly coexist 1% Sn and embodiment E-7 of P (V).
In addition, as shown in Table 14, according to the result of the Strong dielectric film of embodiment E-10～embodiment E-18 and Comparative Example E-7, even change stabilization agent into diethanolamine, also can confirm to add the effect that Sn produces.
And then, according to the result of the Strong dielectric film of embodiment E-19～embodiment E-27 and Comparative Example E-8, change dry air into even if will burn till atmosphere, also can confirm to add the effect that Sn produces.
The Strong dielectric film of embodiment E-10～embodiment E-27, as the fundamental characteristics excellence of electrical condenser, can be used for the purposes of the film capacitor of high capacity density.
Describe embodiments of the invention F-1～embodiment F-45 and Comparative Example F-1～Comparative Example F-18 below in detail.
< embodiment F-1～embodiment F-5>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various samarium compounds (2 ethyl hexanoic acid samarium, 2 Ethylbutanoic acid samarium, three ethanol samariums, three propyl carbinol samariums, tri acetylacetonato samarium) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< embodiment F-6～embodiment F-10>
In sol gel solution, add the various samarium compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment F-1～embodiment F-5.
< embodiment F-11～embodiment F-15>
In sol gel solution, add the various samarium compounds of counting 2.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment F-1～embodiment F-5.
< Comparative Example F-1>
In sol gel solution, do not add samarium compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment F-1～embodiment F-5.
< Comparative Example F-2～Comparative Example F-6>
In sol gel solution, add the various samarium compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment F-1～embodiment F-5.
< embodiment F-16～embodiment F-20>
First, in reaction vessel, add four zirconium-n-butylates and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various samarium compounds (2 ethyl hexanoic acid samarium, 2 Ethylbutanoic acid samarium, three ethanol samariums, three propyl carbinol samariums, tri acetylacetonato samarium) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< embodiment F-21～embodiment F-25>
In sol gel solution, add the various samarium compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment F-16～embodiment F-20.
< embodiment F-26～embodiment F-30>
In sol gel solution, add the various samarium compounds of counting 2.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment F-16～embodiment F-20.
< Comparative Example F-7>
In sol gel solution, do not add samarium compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment F-16～embodiment F-20.
< Comparative Example F-8～12>
In sol gel solution, add the various samarium compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment F-16～embodiment F-20.
< embodiment F-31～embodiment F-35>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various samarium compounds (2 ethyl hexanoic acid samarium, 2 Ethylbutanoic acid samarium, three ethanol samariums, three propyl carbinol samariums, tri acetylacetonato samarium) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in dry air atmosphere, burn till the Strong dielectric film of formation thickness 270nm by the RTA (instant heating treatment unit) of 1 minute at 700 DEG C.
< embodiment F-36～embodiment F-40>
In sol gel solution, add the various samarium compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment F-31～embodiment F-35.
< embodiment F-41～embodiment F-45>
In sol gel solution, add the various samarium compounds of counting 2.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment F-31～embodiment F-35.
< Comparative Example F-13>
In sol gel solution, do not add samarium compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment F-31～embodiment F-35.
< Comparative Example F-14～18>
In sol gel solution, add the various samarium compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment F-31～embodiment F-35.
< comparative evaluation >
For the formation obtaining in embodiment F-1～embodiment F-45 and Comparative Example F-1～Comparative Example F-18 substrate of Strong dielectric film, use metal mask, make the Pt upper electrode of approximately 250 μ m by sputtering at surface, between the Pt lower electrode under Strong dielectric film with frequency 1kHz in the scope inner evaluation C-V of-5～5V characteristic (voltage-dependent of electrostatic capacity), calculate relative permittivity ε r by the maximum value of electrostatic capacity.It should be noted that, the mensuration of C-V characteristic is used the 4284A precision processed LCR meter of Hewlett-Packard Corporation, under Bias step 0.1V, Frequency 1kHz, Oscillation level 30mV, Delay time 0.2sec, Temperature23 DEG C, the condition of Hygrometry 50 ± 10%, measures.Its result is shown in to following table 15～table 17.
[table 15]
[table 16]
[table 17]
From table 15～table 17, with not containing compared with the PZT Strong dielectric film of Comparative Example F-1 of Sm, Comparative Example F-7, Comparative Example F-13, added the Strong dielectric film of embodiment F-1～embodiment F-45 of 0.5%～2%Sm and confirmed high electrostatic capacity and high relative dielectric constant with the thin thickness in 270nm left and right.Judged that by this result the Strong dielectric film of embodiment F-1～embodiment F-45 is as the fundamental characteristics excellence of electrical condenser.
But the Strong dielectric film that has added Comparative Example F-2～Comparative Example F-6, Comparative Example F-8～Comparative Example F-12, Comparative Example F-14～Comparative Example F-18 of 3%Sm obtains than the low result of PZT Strong dielectric film of Comparative Example F-1 containing Sm, Comparative Example F-7, Comparative Example F-13 not.
In addition, according to embodiment F-1～embodiment F-45 that the addition of Sm is changed and Comparative Example F-2～Comparative Example F-6, Comparative Example F-8～Comparative Example F-12, the result of the Strong dielectric film of Comparative Example F-14～Comparative Example F-18, 2% embodiment F-11～embodiment F-15 are added, embodiment F-26～embodiment F-30, the result of embodiment F-41～embodiment F-45 is high especially, then, 1% embodiment F-6～embodiment F-10 are added, embodiment F-21～embodiment F-25, the result of embodiment F-36～embodiment F-40, 0.5% embodiment F-1～embodiment F-5 are added, embodiment F-16～embodiment F-20, the result of embodiment F-31～embodiment F-35 is taken second place, 3% Comparative Example F-2～Comparative Example F-6 are added, Comparative Example F-8～Comparative Example F-12, the result of Comparative Example F-14～Comparative Example F-18 is low.
Be there is the scope of the suitable Sm addition that can contribute to electrostatic capacity and relative permittivity ε r raising by this results verification.
The Strong dielectric film of embodiment F-1～embodiment F-45 forms the fundamental characteristics excellence as electrical condenser with the formation method of composition, Strong dielectric film and the Strong dielectric film that forms by the method, can be used in the purposes of the film capacitor of high capacity density.
Describe embodiments of the invention G-1～embodiment G-45 and comparative example G-1～comparative example G-18 below in detail.
< embodiment G-1～embodiment G-5>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various neodymium compounds (2 ethyl hexanoic acid neodymium, 2 Ethylbutanoic acid neodymium, three ethanol neodymiums, three propyl carbinol neodymiums, tri acetylacetonato neodymium) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< embodiment G-6～embodiment G-10>
In sol gel solution, add the various neodymium compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment G-1～embodiment G-5.
< embodiment G-11～embodiment G-15>
In sol gel solution, add the various neodymium compounds of counting 2.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment G-1～embodiment G-5.
< comparative example G-1>
In sol gel solution, do not add neodymium compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment G-1～embodiment G-5.
< comparative example G-2～6>
In sol gel solution, add the various neodymium compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment G-1～embodiment G-5.
< embodiment G-16～embodiment G-20>
First, in reaction vessel, add four zirconium-n-butylates and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various neodymium compounds (2 ethyl hexanoic acid neodymium, 2 Ethylbutanoic acid neodymium, three ethanol neodymiums, three propyl carbinol neodymiums, tri acetylacetonato neodymium) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< embodiment G-21～embodiment G-25>
In sol gel solution, add the various neodymium compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment G-16～embodiment G-20.
< embodiment G-26～embodiment G-30>
In sol gel solution, add the various neodymium compounds of counting 2.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment G-16～embodiment G-20.
< comparative example G-7>
In sol gel solution, do not add neodymium compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment G-16～embodiment G-20.
< comparative example G-8～comparative example G-12>
In sol gel solution, add the various neodymium compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment G-16～embodiment G-20.
< embodiment G-31～embodiment G-35>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various neodymium compounds (2 ethyl hexanoic acid neodymium, 2 Ethylbutanoic acid neodymium, three ethanol neodymiums, three propyl carbinol neodymiums, tri acetylacetonato neodymium) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in dry air atmosphere, burn till the Strong dielectric film of formation thickness 270nm by the RTA (instant heating treatment unit) of 1 minute at 700 DEG C.
< embodiment G-36～embodiment G-40>
In sol gel solution, add the various neodymium compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment G-31～embodiment G-35.
< embodiment G-41～embodiment G-45>
In sol gel solution, add the various neodymium compounds of counting 2.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment G-31～embodiment G-35.
< comparative example G-13>
In sol gel solution, do not add neodymium compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment G-31～embodiment G-35.
< comparative example G-14～comparative example G-18>
In sol gel solution, add the various neodymium compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment G-31～embodiment G-35.
< comparative evaluation >
For the formation obtaining in embodiment G-1～embodiment G-45 and comparative example G-1～comparative example G-18 the substrate of Strong dielectric film, use metal mask, make the Pt upper electrode of approximately 250 μ m by sputtering at surface, between the Pt lower electrode under Strong dielectric film with frequency 1kHz in the scope inner evaluation C-V of-5～5V characteristic (voltage-dependent of electrostatic capacity), calculate relative permittivity ε r by the maximum value of electrostatic capacity.It should be noted that, the mensuration of C-V characteristic is used the 4284A precision processed LCR meter of Hewlett-Packard Corporation, under Bias step 0.1V, Frequency 1kHz, Oscillation level 30mV, Delay time 0.2sec, Temperature23 DEG C, the condition of Hygrometry 50 ± 10%, measures.Its result is shown in to following table 18～table 20.
[table 18]
[table 19]
[table 20]
From table 18～table 20, with not containing compared with the PZT Strong dielectric film of comparative example G-1, the comparative example G-7 of Nd, comparative example G-13, added the Strong dielectric film of embodiment G-1～embodiment G-45 of 0.5%～2%Nd and confirmed high electrostatic capacity and high relative dielectric constant with the thin thickness in 270nm left and right.Judge that by this result the Strong dielectric film of embodiment G-1～embodiment G-45 is as the fundamental characteristics excellence of electrical condenser.
But the Strong dielectric film that has added comparative example G-2～comparative example G-6, comparative example G-8～comparative example G-12, the comparative example G-14～comparative example G-18 of 3%Nd is than not comparative example G-1, the comparative example G-7 containing Nd, the low result of PZT Strong dielectric film of comparative example G-13.
In addition, according to comparative example G-1～comparative example G-45 that the addition of Nd is changed and comparative example G-2～comparative example G-6, comparative example G-8～comparative example G-12, the result of the Strong dielectric film of comparative example G-14～comparative example G-18, add embodiment G-6～embodiment G-10 of 1%, embodiment G-21～embodiment G-25, the result of embodiment G-36～embodiment G-40 is high especially, then, add embodiment G-1～embodiment G-5 of 0.5%, embodiment G-16～embodiment G-20, embodiment G-31～embodiment G-35 and added embodiment G-11～embodiment G-15 of 2%, embodiment G-26～embodiment G-30, the result that the result of embodiment G-41～embodiment G-45 is basic identical degree, add comparative example G-2～comparative example G-6 of 3%, comparative example G-8～comparative example G-12, the result of comparative example G-14～comparative example G-18 is low.
By this results verification there is the scope that can contribute to the suitable Nd addition that electrostatic capacity and relative permittivity ε r improve.
The Strong dielectric film of embodiment G-1～embodiment G-45 forms the fundamental characteristics excellence as electrical condenser with the formation method of composition, Strong dielectric film and the Strong dielectric film that forms by the method, can be used in the purposes of the film capacitor of high capacity density.
Then describe embodiments of the invention H-1～embodiment H-45 and Comparative Example H-1～Comparative Example H-18 in detail.
< embodiment H-1～embodiment H-5>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various yttrium compounds (2 ethyl hexanoic acid yttrium, 2 Ethylbutanoic acid yttrium, three ethanol yttriums, three propyl carbinol yttriums, tri acetylacetonato yttrium) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< embodiment H-6～embodiment H-10>
In sol gel solution, add the various yttrium compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment H-1～embodiment H-5.
< embodiment H-11～embodiment H-15>
In sol gel solution, add the various yttrium compounds of counting 2.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment H-1～embodiment H-5.
< Comparative Example H-1>
In sol gel solution, do not add yttrium compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment H-1～embodiment H-5.
< Comparative Example H-2～Comparative Example H-6>
In sol gel solution, add the various yttrium compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment H-1～embodiment H-5.
< embodiment H-16～embodiment H-20>
First, in reaction vessel, add four zirconium-n-butylates and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various yttrium compounds (2 ethyl hexanoic acid yttrium, 2 Ethylbutanoic acid yttrium, three ethanol yttriums, three propyl carbinol yttriums, tri acetylacetonato yttrium) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< embodiment H-21～embodiment H-25>
In sol gel solution, add the various yttrium compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment H-16～embodiment H-20.
< embodiment H-26～embodiment H-30>
In sol gel solution, add the various yttrium compounds of counting 2.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment H-16～embodiment H-20.
< Comparative Example H-7>
In sol gel solution, do not add yttrium compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment H-16～embodiment H-20.
< Comparative Example H-8～12>
In sol gel solution, add the various yttrium compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment H-16～embodiment H-20.
< embodiment H-31～embodiment H-35>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various yttrium compounds (2 ethyl hexanoic acid yttrium, 2 Ethylbutanoic acid yttrium, three ethanol yttriums, three propyl carbinol yttriums, tri acetylacetonato yttrium) of counting 0.5mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in dry air atmosphere, burn till the Strong dielectric film of formation thickness 270nm by the RTA (instant heating treatment unit) of 1 minute at 700 DEG C.
< embodiment H-36～embodiment H-40>
In sol gel solution, add the various yttrium compounds of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment H-31～embodiment H-35.
< embodiment H-41～embodiment H-45>
In sol gel solution, add the various yttrium compounds of counting 2.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment H-31～embodiment H-35.
< Comparative Example H-13>
In sol gel solution, do not add yttrium compound, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment H-31～embodiment H-35.
< Comparative Example H-14～Comparative Example H-18>
In sol gel solution, add the various yttrium compounds of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with embodiment H-31～embodiment H-35.
< comparative evaluation >
For the formation obtaining in embodiment H-1～embodiment H-45 and Comparative Example H-1～Comparative Example H-18 substrate of Strong dielectric film, use metal mask, make the Pt upper electrode of approximately 250 μ m by sputtering at surface, between the Pt lower electrode under Strong dielectric film with frequency 1kHz in the scope inner evaluation C-V of-5～5V characteristic (voltage-dependent of electrostatic capacity), calculate relative permittivity ε r by the maximum value of electrostatic capacity.It should be noted that, the mensuration of C-V characteristic is used the 4284A precision processed LCR meter of Hewlett-Packard Corporation, under Bias step 0.1V, Frequency 1kHz, Oscillation level 30mV, Delay time 0.2sec, Temperature23 DEG C, the condition of Hygrometry 50 ± 10%, measures.Its result is shown in to following table 21～table 23.
[table 21]
[table 22]
[table 23]
From table 21～table 23, with not containing compared with the PZT Strong dielectric film of Comparative Example H-1 of Y (yttrium), Comparative Example H-7, Comparative Example H-13, added the Strong dielectric film of embodiment H-1～embodiment H-45 of 0.5%～2%Y (yttrium) and confirmed high electrostatic capacity and high relative dielectric constant with the thin thickness in 270nm left and right.Judge that by this result the Strong dielectric film of embodiment H-1～embodiment H-45 is as the fundamental characteristics excellence of electrical condenser.
But the Strong dielectric film that has added Comparative Example H-2～Comparative Example H-6, Comparative Example H-8～Comparative Example H-12, Comparative Example H-14～Comparative Example H-18 of Y (yttrium) is than the low result of PZT Strong dielectric film of Comparative Example H-1 containing Y (yttrium), Comparative Example H-7, Comparative Example H-13 not.
In addition, according to embodiment H-1～embodiment H-45 and Comparative Example H-2～Comparative Example H-6 that the addition of Y (yttrium) is changed, Comparative Example H-8～Comparative Example H-12, the result of the Strong dielectric film of Comparative Example H-14～Comparative Example H-18, add embodiment H-6～embodiment H-10 of 1%, embodiment H-21～embodiment H-25, the result of embodiment H-36～embodiment H-40 is high especially, then, add embodiment H-1～embodiment H-5 of 0.5%, embodiment H-16～embodiment H-20, embodiment H-31～embodiment H-35 and added embodiment H-11～embodiment H-15 of 2%, embodiment H-26～embodiment H-30, the result that the result of embodiment H-41～embodiment H-45 is basic identical degree, 3% Comparative Example H-2～Comparative Example H-6 are added, Comparative Example H-8～Comparative Example H-12, the result of Comparative Example H-14～Comparative Example H-18 is low.
By this results verification there is the scope that can contribute to suitable Y (yttrium) addition that electrostatic capacity and relative permittivity ε r improve.
The Strong dielectric film of embodiment H-1～embodiment H-45 forms the fundamental characteristics excellence as electrical condenser with the formation method of composition, Strong dielectric film and the Strong dielectric film that forms by the method, can be used in the purposes of the film capacitor of high capacity density.
[the 3rd group]
Describe embodiments of the invention I-1～example I-75 and Comparative Example I-1～Comparative Example I-9 below in detail.
< example I-1～example I-5>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various carboxylic acids (2 ethyl hexanoic acid, 3-ethyl valeric acid, 2 Ethylbutanoic acid, isovaleric acid, butanic acid) of counting 0.1mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< example I-6～example I-10>
In sol gel solution, add the various carboxylic acids of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-1～example I-5.
< example I-11～example I-15>
In sol gel solution, add the various carboxylic acids of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-1～example I-5.
< example I-16～example I-20>
In sol gel solution, add the various carboxylic acids of counting 5.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-1～example I-5.
< example I-21～example I-25>
In sol gel solution, add the various carboxylic acids of counting 10.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-1～example I-5.
< Comparative Example I-1>
In sol gel solution, do not add various carboxylic acids, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-1～example I-5.
< Comparative Example I-2>
In sol gel solution, add the propionic acid of counting 5.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-1～example I-5.
< Comparative Example I-3>
In sol gel solution, add the n-caprylic acid of counting 5.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-1～example I-5.
< example I-26～example I-30>
First, in reaction vessel, add four zirconium-n-butylates and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the diethanolamine as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various carboxylic acids (2 ethyl hexanoic acid, 3-ethyl valeric acid, 2 Ethylbutanoic acid, isovaleric acid, butanic acid) of counting 0.1mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in 100% oxygen atmosphere by 700 DEG C at the RTA (instant heating treatment unit) of 1 minute burn till, the Strong dielectric film of formation thickness 270nm.
< example I-31～example I-35>
In sol gel solution, add the various carboxylic acids of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-26～example I-30.
< example I-36～example I-40>
In sol gel solution, add the various carboxylic acids of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-26～example I-30.
< example I-41～example I-45>
In sol gel solution, add the various carboxylic acids of counting 5.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-26～example I-30.
< example I-46～example I-50>
In sol gel solution, add the various carboxylic acids of counting 10.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-26～example I-30.
< Comparative Example I-4>
In sol gel solution, do not add various carboxylic acids, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-26～example I-30.
< Comparative Example I-5>
In sol gel solution, add the propionic acid of counting 5.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-26～example I-30.
< Comparative Example I-6>
In sol gel solution, add the n-caprylic acid of counting 5.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-26～example I-30.
< example I-51～example I-55>
First, in reaction vessel, add four zirconium-n-butylates and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Add therein titanium tetraisopropylate and the methyl ethyl diketone as stabilization agent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, add therein lead acetate 3 hydrates and the propylene glycol as solvent, under nitrogen atmosphere, reflux in the temperature of 150 DEG C.Then, at 150 DEG C, carry out underpressure distillation, remove by product, and then add propylene glycol, carry out concentration adjustment, obtain thus with the convert liquid of the metallic compound that contains 30 quality % concentration of oxide compound.And then, dilute alcohol by interpolation, obtain the sol gel solution taking the each metal ratio of oxide compound conversion as the metallic compound that contains 10 quality % concentration of Pb/Zr/Ti=110/52/48.
Then, by sol gel solution 5 deciles, in above-mentioned sol gel solution, add respectively the various carboxylic acids (2 ethyl hexanoic acid, 3-ethyl valeric acid, 2 Ethylbutanoic acid, isovaleric acid, butanic acid) of counting 0.1mol% with hair ratio, obtain thus 5 kinds of film formation solution.
Use above-mentioned 5 kinds of film formation solution, utilize CSD method to carry out the formation of film by following method., under 500rpm, be 3 seconds by spin-coating method, then under 3000rpm, be 6 inches of silicon substrate (Pt/TiO that under the condition in 15 seconds, each solution coat formed to Pt film on surface by sputter 2/ SiO 2/ Si (100) substrate) on.Next, use hot plate, at 350 DEG C, heat 5 minutes, carry out pre-fired.The operation of this coating, pre-fired is repeated after 6 times, in dry air atmosphere, burn till the Strong dielectric film of formation thickness 270nm by the RTA (instant heating treatment unit) of 1 minute at 700 DEG C.
< example I-56～example I-60>
In sol gel solution, add the various carboxylic acids of counting 1.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-51～example I-55.
< example I-61～example I-65>
In sol gel solution, add the various carboxylic acids of counting 3.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-51～example I-55.
< example I-66～example I-70>
In sol gel solution, add the various carboxylic acids of counting 5.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-51～example I-55.
< example I-71～75>
In sol gel solution, add the various carboxylic acids of counting 10.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-51～example I-55.
< Comparative Example I-7>
In sol gel solution, do not add various carboxylic acids, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-51～example I-55.
< Comparative Example I-8>
In sol gel solution, add the propionic acid of counting 5.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-51～example I-55.
< Comparative Example I-9>
In sol gel solution, add the n-caprylic acid of counting 5.0mol% with hair ratio, make film formation solution, in addition, similarly on substrate, form Strong dielectric film with example I-51～example I-55.
< comparative evaluation >
For the formation obtaining in example I-1～example I-75 and Comparative Example I-1～Comparative Example I-9 substrate of Strong dielectric film, use metal mask, make the Pt upper electrode of approximately 250 μ m by sputtering at surface, between the Pt lower electrode under Strong dielectric film with frequency 1kHz in the scope inner evaluation C-V of-5～5V characteristic (voltage-dependent of electrostatic capacity), calculate relative permittivity ε r by the maximum value of electrostatic capacity.It should be noted that, the mensuration of C-V characteristic is used the 4284A precision processed LCR meter of Hewlett-Packard Corporation, under Bias step 0.1V, Frequency 1kHz, Oscillation level 30mV, Delay time 0.2sec, Temperature23 DEG C, the condition of Hygrometry 50 ± 10%, measures.The results are shown in following table 24～table 26.
[table 24]
[table 25]
[table 26]
From table 24～table 26, with Comparative Example I-1 that does not contain carboxylic acid, Comparative Example I-4, the PZT Strong dielectric film of Comparative Example I-7 and Comparative Example I-2 of having added coordination and do not form on metal time the carboxylic acid of the kind of six-membered ring structure, Comparative Example I-3, Comparative Example I-5, Comparative Example I-6, the PZT Strong dielectric film of Comparative Example I-8 and Comparative Example I-9 is compared, add the Strong dielectric film that 0.1%～10% coordination can form example I-1～example I-75 of the carboxylic acid of six-membered ring structure on metal time and confirmed high electrostatic capacity and high relative dielectric constant with the thin thickness in 270nm left and right.Judged that by this result the Strong dielectric film of example I-1～example I-75 is as the fundamental characteristics excellence of electrical condenser.
In addition, according to the result that has changed coordination and can form on metal time the Strong dielectric film of example I-1～example I-75 of the addition of the carboxylic acid of six-membered ring structure, 5% example I-16～example I-20 are added, example I-41～example I-45, the result of example I-66～example I-70 is high especially, then, 10% example I-21～example I-25 are added, example I-46～example I-50, the result of example I-71～example I-75, 3% example I-11～example I-15 are added, example I-36～example I-40, the result of example I-61～example I-65 is taken second place, 1% example I-6～example I-10 are added, example I-31～example I-35, the result of example I-56～example I-60 and added 0.1% example I-1～example I-5, example I-26～example I-30, the result of example I-51～example I-55 is minimum.
By this results verification when adding coordination and can forming the carboxylic acid of six-membered ring structure on metal time, existence can contribute to the scope of the suitable addition that electrostatic capacity and relative permittivity ε r improve.
The Strong dielectric film of example I-1～example I-75 forms the fundamental characteristics excellence as electrical condenser with the formation method of composition, Strong dielectric film and the Strong dielectric film that forms by the method, can be used for the purposes such as film capacitor of high capacity density.
The preferred embodiment of the present invention has more than been described, but the present invention is not limited to above-mentioned embodiment.Increase, omission, displacement and other changes that in the scope that does not depart from purport of the present invention, can form.The present invention is not limited to above-mentioned explanation, only by the circumscription of the claims that attach.
Industrial applicability
Strong dielectric film of the present invention forms and can be used in electrical condenser, IPD, the DRAM complex electronic device such as electrical condenser, stacked capacitor, transistorized isolator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer with the formation method of composition, Strong dielectric film and the Strong dielectric film that forms by the method.

Claims (14)

1. a Strong dielectric film formation composition, for being used to form the Strong dielectric film formation composition of the a kind of Strong dielectric film that is selected from PLZT, PZT and PT, it is characterized in that, be to be used to form the fluid composition of taking the film that mixes complex metal oxides form, described mixing complex metal oxides is in general formula (1): (Pb xla y) (Zr zti (1-z)) O 3in the complex metal oxides A representing, mix to comprise and be selected from that the one kind or two or more composite oxides B of Si, Ce and Bi obtains, 0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9 in formula (1)
Comprise raw material for forming above-mentioned complex metal oxides A and for the raw material that forms above-mentioned composite oxides B the organometallic compound solution can provide the ratio of the above-mentioned general formula atoms metal that (1) represents ratio to be dissolved in organic solvent,
The compound of organic group via its oxygen or nitrogen-atoms and metallic element bonding for the raw material that forms complex metal oxides A,
When composite oxides B contains Si, the mol ratio B/A of composite oxides B and complex metal oxides A is 0 < B/A < 0.1,
When composite oxides B contains Ce, the mol ratio B/A of composite oxides B and complex metal oxides A is 0 < B/A < 0.05,
When composite oxides B contains Bi, the mol ratio B/A of composite oxides B and complex metal oxides A is 0 < B/A < 0.2.
2. Strong dielectric film formation composition as claimed in claim 1, wherein, be selected from metal alkoxide, metal glycol coordination compound, metal triol coordination compound, metal carboxylate, metal beta-diketon coordination compound, metal beta-diketo-ester coordination compound, metal β-imino-ketone coordination compound and metal amino coordination compound one kind or two or more for forming the raw material of complex metal oxides A.
3. Strong dielectric film formation composition as claimed in claim 1 wherein, is to contain one kind or two or more, the organic group that is selected from Si, Ce and Bi via the compound of its oxygen or nitrogen-atoms and metallic element bonding for forming the raw material of composite oxides B.
4. Strong dielectric film formation composition as claimed in claim 3, wherein, contain and be selected from the one kind or two or more of Si, Ce and Bi for the raw material that forms composite oxides B, be selected from the one kind or two or more of metal alkoxide, metal glycol coordination compound, metal triol coordination compound, metal carboxylate, metal beta-diketon coordination compound, metal beta-diketo-ester coordination compound, metal β-imino-ketone coordination compound and metal amino coordination compound.
5. Strong dielectric film formation composition as claimed in claim 1, wherein, further contain taking the ratio of 1 mole as 0.2～3 mole of the total metal content with respect in composition the one kind or two or more stabilization agent that is selected from beta-diketon, beta-keto acid, 'beta '-ketoester, alcohol acid, glycol, triol, high carboxylic acid, alkanolamine and polyamine.
6. Strong dielectric film formation composition as claimed in claim 1, wherein, above-mentioned organic solvent is to be selected from one kind or two or more in carboxylic acid, alcohol, ester, ketone, ethers, naphthenic, the fragrant same clan and tetrahydrofuran (THF).
7. Strong dielectric film formation composition as claimed in claim 1, wherein, composite oxides B contains Si, and above-mentioned organic solvent contains propylene glycol.
8. Strong dielectric film formation composition as claimed in claim 1, wherein, composite oxides B contains Si, and the mol ratio B/A of composite oxides B and complex metal oxides A is 0.005≤B/A≤0.05.
9. Strong dielectric film formation composition as claimed in claim 1, composite oxides B contains Ce, and the mol ratio B/A of composite oxides B and complex metal oxides A is 0.005≤B/A≤0.03.
10. Strong dielectric film formation composition as claimed in claim 1, wherein, composite oxides B contains Bi, and the mol ratio B/A of composite oxides B and complex metal oxides A is 0.005≤B/A≤0.1.
The formation method of 11. 1 kinds of Strong dielectric films, it is characterized in that, Strong dielectric film formation claimed in claim 1 is coated to heat resistant substrate with composition, in air, in oxidation atmosphere or the operation that heats in containing water vapor atmosphere carry out 1 time or repeat to the film that can obtain desired thickness, at least adding in final operation hanker or heat after this film is burnt till more than crystallized temperature.
12. 1 kinds of Strong dielectric films are Strong dielectric films that thickness that the method by described in claim 11 forms is 50～500nm.
The complex electronic device of 13. film capacitors with the Strong dielectric film described in claim 12, electrical condenser, IPD, DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer.
The complex electronic device corresponding to the film capacitor above frequency band of 100MHz, that there is Strong dielectric film, electrical condenser, IPD, DRAM electrical condenser, stacked capacitor, transistorized gate insulator, nonvolatile memory, current pyroelectric infrared measuring element, piezoelectric element, electrical optical elements, stimulator, resonon, ultrasonic motor or LC noise filter element for storer described in 14. claims 13.
CN200980119294.7A 2008-05-28 2009-05-28 Composition for ferroelectric thin film formation, method for ferroelectric thin film formation, and ferroelectric thin film formed by the method Active CN102046563B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201310273420.2A CN103360066B (en) 2008-05-28 2009-05-28 The formation method of Strong dielectric film formation composition, Strong dielectric film and the Strong dielectric film formed by the method
CN201410553563.3A CN104446463B (en) 2008-05-28 2009-05-28 Composition for ferroelectric thin film formation, method for ferroelectric thin film formation, and ferroelectric thin film formed by the method

Applications Claiming Priority (43)

Application Number Priority Date Filing Date Title
JP2008139623 2008-05-28
JP2008-139641 2008-05-28
JP2008139641 2008-05-28
JP2008-139623 2008-05-28
JP2008282849 2008-11-04
JP2008-282849 2008-11-04
JP2008328101 2008-12-24
JP2008-328101 2008-12-24
JP2009009819 2009-01-20
JP2009009818 2009-01-20
JP2009-009819 2009-01-20
JP2009-009818 2009-01-20
JP2009022638 2009-02-03
JP2009-022638 2009-02-03
JP2009022641 2009-02-03
JP2009-022641 2009-02-03
JP2009023280 2009-02-04
JP2009023278 2009-02-04
JP2009-023280 2009-02-04
JP2009-023278 2009-02-04
JP2009025683 2009-02-06
JP2009-025683 2009-02-06
JP2009-025681 2009-02-06
JP2009025681 2009-02-06
JP2009-059019 2009-03-12
JP2009059019A JP5655272B2 (en) 2009-03-12 2009-03-12 Composition for forming ferroelectric thin film, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method
JP2009-060348 2009-03-13
JP2009060348A JP5659457B2 (en) 2009-03-13 2009-03-13 Composition for forming ferroelectric thin film, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method
JP2009-085830 2009-03-31
JP2009085819A JP5655274B2 (en) 2009-03-31 2009-03-31 Composition for forming ferroelectric thin film, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method
JP2009-085819 2009-03-31
JP2009085830A JP5293347B2 (en) 2008-12-24 2009-03-31 Composition for forming ferroelectric thin film, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method
JP2009-102815 2009-04-21
JP2009-102817 2009-04-21
JP2009102815A JP5526591B2 (en) 2009-01-20 2009-04-21 Composition for forming ferroelectric thin film, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method
JP2009102817A JP5417962B2 (en) 2009-01-20 2009-04-21 Composition for forming ferroelectric thin film, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method
JP2009105076A JP5591484B2 (en) 2008-11-04 2009-04-23 Composition for forming ferroelectric thin film, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method
JP2009-105076 2009-04-23
JP2009105883A JP5526593B2 (en) 2008-05-28 2009-04-24 Composition for forming ferroelectric thin film, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method
JP2009-105885 2009-04-24
JP2009105885A JP5591485B2 (en) 2008-05-28 2009-04-24 Composition for forming ferroelectric thin film, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method
JP2009-105883 2009-04-24
PCT/JP2009/059804 WO2009145272A1 (en) 2008-05-28 2009-05-28 Composition for ferroelectric thin film formation, method for ferroelectric thin film formation, and ferroelectric thin film formed by the method

Related Child Applications (3)

Application Number Title Priority Date Filing Date
CN201110025514.9A Division CN102173795B (en) 2008-05-28 2009-05-28 Composition for ferroelectric thin film formation, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method thereof
CN201410553563.3A Division CN104446463B (en) 2008-05-28 2009-05-28 Composition for ferroelectric thin film formation, method for ferroelectric thin film formation, and ferroelectric thin film formed by the method
CN201310273420.2A Division CN103360066B (en) 2008-05-28 2009-05-28 The formation method of Strong dielectric film formation composition, Strong dielectric film and the Strong dielectric film formed by the method

Publications (2)

Publication Number Publication Date
CN102046563A CN102046563A (en) 2011-05-04
CN102046563B true CN102046563B (en) 2014-08-06

Family

ID=43596929

Family Applications (4)

Application Number Title Priority Date Filing Date
CN201310273420.2A Active CN103360066B (en) 2008-05-28 2009-05-28 The formation method of Strong dielectric film formation composition, Strong dielectric film and the Strong dielectric film formed by the method
CN200980119294.7A Active CN102046563B (en) 2008-05-28 2009-05-28 Composition for ferroelectric thin film formation, method for ferroelectric thin film formation, and ferroelectric thin film formed by the method
CN201410553563.3A Active CN104446463B (en) 2008-05-28 2009-05-28 Composition for ferroelectric thin film formation, method for ferroelectric thin film formation, and ferroelectric thin film formed by the method
CN201110025514.9A Active CN102173795B (en) 2008-05-28 2009-05-28 Composition for ferroelectric thin film formation, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method thereof

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201310273420.2A Active CN103360066B (en) 2008-05-28 2009-05-28 The formation method of Strong dielectric film formation composition, Strong dielectric film and the Strong dielectric film formed by the method

Family Applications After (2)

Application Number Title Priority Date Filing Date
CN201410553563.3A Active CN104446463B (en) 2008-05-28 2009-05-28 Composition for ferroelectric thin film formation, method for ferroelectric thin film formation, and ferroelectric thin film formed by the method
CN201110025514.9A Active CN102173795B (en) 2008-05-28 2009-05-28 Composition for ferroelectric thin film formation, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method thereof

Country Status (5)

Country Link
US (5) US8859051B2 (en)
EP (3) EP2343268B1 (en)
KR (2) KR101565186B1 (en)
CN (4) CN103360066B (en)
WO (1) WO2009145272A1 (en)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011089748A1 (en) * 2010-01-21 2011-07-28 株式会社ユーテック Pbnzt ferroelectric film, sol-gel solution, film forming method, and method for producing ferroelectric film
JP5533622B2 (en) * 2010-04-14 2014-06-25 三菱マテリアル株式会社 Composition for forming ferroelectric thin film, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method
EP2426684A1 (en) 2010-09-02 2012-03-07 Mitsubishi Materials Corporation Dielectric-thin-film forming composition, method of forming dielectric thin film, and dielectric thin film formed by the method
EP2688116B1 (en) 2011-03-15 2016-06-08 Konica Minolta, Inc. Ferroelectric thin film and method for producing same
JP2013136502A (en) * 2011-11-28 2013-07-11 Mitsubishi Materials Corp Composition for forming ferroelectric thin film, method for forming the thin film, and thin film formed by the method
EP2608219B1 (en) * 2011-12-20 2015-03-04 Mitsubishi Materials Corporation Dielectric thin film-forming composition, method of forming dielectric thin film and dielectric thin film formed by the method
JP5929654B2 (en) * 2012-09-11 2016-06-08 三菱マテリアル株式会社 Ferroelectric thin film forming composition and method for forming the thin film
JP5793525B2 (en) * 2013-03-08 2015-10-14 株式会社東芝 Nonvolatile semiconductor memory device
JP2014177359A (en) 2013-03-13 2014-09-25 Ricoh Co Ltd Complex oxide, thin film capacitive element, droplet discharge head, and method for producing complex oxide
JP6167657B2 (en) * 2013-05-13 2017-07-26 三菱マテリアル株式会社 Silicon substrate with ferroelectric film
JP6237398B2 (en) 2014-03-27 2017-11-29 三菱マテリアル株式会社 Ce-doped PZT-based piezoelectric film forming composition
JP6237399B2 (en) * 2014-03-27 2017-11-29 三菱マテリアル株式会社 Ce-doped PZT piezoelectric film
CN103943358B (en) * 2014-03-28 2017-01-18 张海鹏 Thinning agent for thinning chip capacitor sizing agent
CN105428530B (en) * 2015-12-17 2018-07-03 中山大学 A kind of resistance switch performance can pass through PLT films of mechanical loading regulation and control and preparation method thereof
JP6665673B2 (en) * 2016-05-12 2020-03-13 三菱マテリアル株式会社 Manufacturing method of ferroelectric thin film
CN110447093B (en) * 2017-02-22 2023-04-25 出光兴产株式会社 Oxide semiconductor film, thin film transistor, oxide sintered body, and sputtering target
CN108358630B (en) * 2018-03-15 2021-05-25 中国科学院上海硅酸盐研究所 High-energy-storage-density antiferroelectric ceramic material and preparation method thereof
CN112062563B (en) * 2020-09-17 2022-05-03 广西大学 Preparation method of PSINT-based high-entropy ferroelectric thin film material
CN112062552A (en) * 2020-09-17 2020-12-11 广西大学 Preparation method of lead-free film material by utilizing phase change induction
KR102399957B1 (en) * 2021-01-25 2022-05-19 강원대학교산학협력단 Manufacturing method of ferroelectric thin film and the same manufactured thereby
CN115206680A (en) * 2022-07-14 2022-10-18 江苏箬竹智能科技有限公司 Efficient fatigue-free solid energy storage thin-film capacitor and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1624468A1 (en) * 2003-04-30 2006-02-08 Asahi Glass Company Ltd. Liquid composition for forming ferroelectric thin film and method for forming ferroelectric thin film
CN1830811A (en) * 2004-03-11 2006-09-13 东京应化工业株式会社 Coating liquid for forming bi-based dielectric thin film with paraelectric and bi-based dielectric thin film

Family Cites Families (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60236404A (en) 1984-05-10 1985-11-25 日本曹達株式会社 Method of producing thin film ferrodielectric material
US4946710A (en) * 1987-06-02 1990-08-07 National Semiconductor Corporation Method for preparing PLZT, PZT and PLT sol-gels and fabricating ferroelectric thin films
US5519234A (en) * 1991-02-25 1996-05-21 Symetrix Corporation Ferroelectric dielectric memory cell can switch at least giga cycles and has low fatigue - has high dielectric constant and low leakage current
US5423285A (en) * 1991-02-25 1995-06-13 Olympus Optical Co., Ltd. Process for fabricating materials for ferroelectric, high dielectric constant, and integrated circuit applications
US5468679A (en) * 1991-02-25 1995-11-21 Symetrix Corporation Process for fabricating materials for ferroelectric, high dielectric constant, and integrated circuit applications
JPH0585704A (en) 1991-03-07 1993-04-06 Olympus Optical Co Ltd Production of ferroelectric thin film
JPH04328817A (en) 1991-04-30 1992-11-17 Sumitomo Chem Co Ltd Manufacture of ceramic thin film with electrode
JP3228776B2 (en) * 1992-02-19 2001-11-12 旭電化工業株式会社 Organic acid titanium compound and method for producing the same
JP3261735B2 (en) 1992-06-09 2002-03-04 セイコーエプソン株式会社 Method for manufacturing dielectric element
US6126743A (en) * 1993-03-12 2000-10-03 Sumitomo Chemical Company, Limited Process for producing dielectrics and fine single crystal powders and thin film capacitor
JPH07252664A (en) * 1994-03-14 1995-10-03 Texas Instr Japan Ltd Formation of ferroelectric film by sol-gel method, manufacture of capacitor using the same, solution of starting material therefor and preparation of solution
JPH08153854A (en) 1994-09-29 1996-06-11 Olympus Optical Co Ltd Manufacture of ferroelectric thin-film capacitor
JP3446461B2 (en) 1995-06-09 2003-09-16 三菱マテリアル株式会社 Composition for forming Ba1-xSrxTiyO3 thin film, method for forming Ba1-xSrxTiyO3 thin film, and method for manufacturing thin-film capacitor
US6066581A (en) * 1995-07-27 2000-05-23 Nortel Networks Corporation Sol-gel precursor and method for formation of ferroelectric materials for integrated circuits
WO1997005994A1 (en) 1995-08-04 1997-02-20 Microcoating Technologies Inc Chemical vapor deposition and powder formation using thermal spray with near supercritical and supercritical fluid solutions
US5849465A (en) * 1996-11-08 1998-12-15 Symetrix Corporation Photosensitive titanium carboxydiketonate and titanium carboxyketoester precursor solutions and method of patterning integrated circuits using the same
JPH10231196A (en) 1996-12-17 1998-09-02 Sony Corp Production of oxide laminated structure, and apparatus for chemical vapor-phase growth of organic metal compound
US5788757A (en) 1996-12-23 1998-08-04 Symetrix Corporation Composition and process using ester solvents for fabricating metal oxide films and electronic devices including the same
JP3475736B2 (en) 1997-09-04 2003-12-08 三菱マテリアル株式会社 Pb-based metal oxide thin film forming solution with excellent stability without change over time
EP1039525A4 (en) 1997-11-10 2002-02-06 Hitachi Ltd Dielectric element and manufacturing method therefor
JP2995290B2 (en) 1998-02-03 1999-12-27 工業技術院長 Method of forming PZT-based ferroelectric thin film
US6203608B1 (en) * 1998-04-15 2001-03-20 Ramtron International Corporation Ferroelectric thin films and solutions: compositions
US6143366A (en) * 1998-12-24 2000-11-07 Lu; Chung Hsin High-pressure process for crystallization of ceramic films at low temperatures
JP2000204487A (en) 1999-01-13 2000-07-25 Kanto Chem Co Inc Coating solution for forming ferroelectric thin film
US6236076B1 (en) * 1999-04-29 2001-05-22 Symetrix Corporation Ferroelectric field effect transistors for nonvolatile memory applications having functional gradient material
US7094284B2 (en) 1999-10-07 2006-08-22 Advanced Technology Materials, Inc. Source reagent compositions for CVD formation of high dielectric constant and ferroelectric metal oxide thin films and method of using same
FR2811317B1 (en) * 2000-07-07 2002-10-11 Thomson Csf CROSSLINKED RESIN AND PROCESS FOR PRODUCING OXIDES USING THE CROSSLINKED RESIN
JP4329287B2 (en) 2000-12-27 2009-09-09 三菱マテリアル株式会社 PLZT or PZT ferroelectric thin film, composition for forming the same and method for forming the same
JP4419332B2 (en) 2001-02-06 2010-02-24 三菱マテリアル株式会社 Substrate surface structure of perovskite oxide film, substrate and perovskite oxide film
KR100416760B1 (en) * 2001-03-12 2004-01-31 삼성전자주식회사 Method for preparing a thick coating of PZT using sol-gel process
US6831313B2 (en) * 2001-05-10 2004-12-14 Symetrix Corporation Ferroelectric composite material, method of making same and memory utilizing same
CN1269215C (en) * 2001-09-05 2006-08-09 精工爱普生株式会社 Ferroelectric memory device and method of manufacturing the same
US7553512B2 (en) * 2001-11-02 2009-06-30 Cabot Corporation Method for fabricating an inorganic resistor
KR100513724B1 (en) 2002-12-24 2005-09-08 삼성전자주식회사 Ferroelectric thin film and preparing method thereof
JP2004277200A (en) 2003-03-13 2004-10-07 Seiko Epson Corp Ferroelectric thin film and method for manufacturing the same
JP4720969B2 (en) 2003-03-28 2011-07-13 セイコーエプソン株式会社 Ferroelectric film, piezoelectric film, ferroelectric memory, and piezoelectric element
JP2005159308A (en) * 2003-11-05 2005-06-16 Seiko Epson Corp Ferroelectric film, ferroelectric capacitor, and ferroelectric memory
JP2005217219A (en) 2004-01-30 2005-08-11 Hitachi Cable Ltd Ferroelectric thin film and manufacturing method thereof
JP4189504B2 (en) 2004-02-27 2008-12-03 キヤノン株式会社 Method for manufacturing piezoelectric thin film
ATE529901T1 (en) * 2004-02-27 2011-11-15 Canon Kk PIEZOELECTRIC THIN FILM, METHOD FOR PRODUCING A PIEZOELECTRIC THIN FILM, PIEZOELECTRIC ELEMENT AND INKJET RECORDING HEAD
KR100749301B1 (en) * 2004-07-07 2007-08-14 주식회사 엘지화학 New organic/inorganic composite porous film and electrochemical device prepared thereby
US8241708B2 (en) * 2005-03-09 2012-08-14 Micron Technology, Inc. Formation of insulator oxide films with acid or base catalyzed hydrolysis of alkoxides in supercritical carbon dioxide
US7446055B2 (en) * 2005-03-17 2008-11-04 Air Products And Chemicals, Inc. Aerosol misted deposition of low dielectric organosilicate films
JP2006282456A (en) 2005-03-31 2006-10-19 Seiko Epson Corp Composition for forming pzt thin film and method for producing pzt thin film
JP2008084581A (en) 2006-09-26 2008-04-10 Dainippon Printing Co Ltd Ferroelectric composition
JP4952445B2 (en) 2007-08-30 2012-06-13 セイコーエプソン株式会社 Printing system and program
JP2009060348A (en) 2007-08-31 2009-03-19 Victor Co Of Japan Ltd Headphone
US8583712B2 (en) 2007-09-18 2013-11-12 Seagate Technology Llc Multi-bit sampling of oscillator jitter for random number generation
JP5210586B2 (en) 2007-10-01 2013-06-12 Ｉｄｅｃ株式会社 Plastic discrimination device and plastic discrimination method
JP2009085830A (en) 2007-10-01 2009-04-23 Toyota Industries Corp Insulation resistance deterioration detector for industrial vehicle
TW200920136A (en) 2007-10-19 2009-05-01 Webs Tv Inc Playing system for showing an external data banner on a media video and playing method thereof
JP2009102817A (en) 2007-10-22 2009-05-14 Takenaka Komuten Co Ltd Soil cement sampling equipment and confirmation method for strength of foot protection of leading end of existing pile
JP5074880B2 (en) 2007-10-22 2012-11-14 トヨタホーム株式会社 Stair safety device and building
JP5326635B2 (en) 2009-02-17 2013-10-30 トヨタ自動車株式会社 Fuel cell system

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1624468A1 (en) * 2003-04-30 2006-02-08 Asahi Glass Company Ltd. Liquid composition for forming ferroelectric thin film and method for forming ferroelectric thin film
CN1830811A (en) * 2004-03-11 2006-09-13 东京应化工业株式会社 Coating liquid for forming bi-based dielectric thin film with paraelectric and bi-based dielectric thin film

Also Published As

Publication number Publication date
US20110098173A1 (en) 2011-04-28
EP2298714B1 (en) 2017-07-05
CN102173795A (en) 2011-09-07
EP2436661B1 (en) 2016-03-30
WO2009145272A1 (en) 2009-12-03
EP2298714A4 (en) 2011-07-06
CN102046563A (en) 2011-05-04
US8859051B2 (en) 2014-10-14
US8790538B2 (en) 2014-07-29
KR101242840B1 (en) 2013-03-13
US9005358B2 (en) 2015-04-14
CN102173795B (en) 2014-12-10
US20110177235A1 (en) 2011-07-21
US20130295414A1 (en) 2013-11-07
EP2343268A1 (en) 2011-07-13
CN103360066B (en) 2015-11-18
KR20110014159A (en) 2011-02-10
US20140349834A1 (en) 2014-11-27
KR101565186B1 (en) 2015-11-02
KR20110015645A (en) 2011-02-16
EP2343268B1 (en) 2018-02-21
US9502636B2 (en) 2016-11-22
CN104446463B (en) 2017-04-12
CN104446463A (en) 2015-03-25
US20140349139A1 (en) 2014-11-27
EP2436661A1 (en) 2012-04-04
EP2298714A1 (en) 2011-03-23
CN103360066A (en) 2013-10-23

Similar Documents

Publication Publication Date Title
CN102046563B (en) Composition for ferroelectric thin film formation, method for ferroelectric thin film formation, and ferroelectric thin film formed by the method
CN103130504A (en) Composition for forming ferroelectric thin film, method for forming ferroelectric thin film, ferroelectric thin film, and complex electronic componen
US10112872B2 (en) Composition for forming Mn and Nb co-doped PZT-based piezoelectric film
KR102007543B1 (en) METHOD OF FORMING PNbZT FERROELECTRIC THIN FILM
WO2015030064A1 (en) METHOD FOR MANUFACTURING PNbZT THIN FILM
KR20160138417A (en) Mn-doped pzt-based piezoelectric film formation composition and mn-doped pzt-based piezoelectric film
TW201601360A (en) Mn and Nb co-doped PZT-based piezoelectric film
JP6183261B2 (en) Mn-doped PZT-based piezoelectric film forming composition
TWI665163B (en) Composition for forming cerium-doped pzt piezoelectric film
JP4407103B2 (en) Ferroelectric thin film with excellent fatigue resistance and composition for forming the same
KR20160138416A (en) Cerium-doped pzt piezoelectric film

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant